JP7629985B2 - Ring-containing polymer compositions obtained using transition metal bis(phenolate) catalyst complexes and methods for their preparation - Patents.com - Google Patents

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of and priority to U.S. Provisional Application No. 63/065,344, filed August 13, 2020, the disclosure of which is incorporated herein by reference.

The present invention relates to the following:
1) USSN 16/788,022, filed February 11, 2020;
2) USSN 16/788,088, filed February 11, 2020;
3) USSN 16/788,124, filed February 11, 2020;
4) USSN 16/787,909, filed February 11, 2020;
5) USSN 16/787,837, filed February 11, 2020;
6) PCT Application No. PCT/US2020/045819, filed August 11, 2020;
7) PCT Application No. PCT/US2020/045820, filed August 11, 2020; and 8) PCT Application No. PCT/US2020/045822, filed August 11, 2020.

FIELD OF THEINVENTION This invention relates to polymer compositions containing cyclic monomers prepared using novel catalyst compounds comprising Group 4 bis(phenolate) complexes, compositions containing same, and methods for making such copolymers.

There has been interest in modifying the structure of polyolefins in hopes of obtaining new and better combinations of properties such as melt strength, stiffness, shrinkage, and optical properties. In addition, high optical clarity, excellent melt strength, bubble stability, and good extrusion properties are important for blown films, such as heat-sealable blown films. However, a wide range of films made from polyethylene compositions still lack certain properties (e.g., excellent tensile and impact strength, puncture resistance, excellent optical properties, and best sealing properties). Improved strength properties, along with excellent stretchability, allow downgauging in blown film applications (e.g., as bags).

Catalyst design, polymer reaction engineering, and polymer process technology have been investigated to produce novel polyolefin materials to meet diversified industrial demands. Catalyst design plays an important role in controlling the molecular structure of polyethylene and therefore the material properties and processability. The polymer market is currently dominated by products prepared with Ziegler-Natta (ZN) type catalysts and metallocene type catalysts. Optimization of these polyethylene products most often involves multiple reactor and/or multiple catalyst processes. Both strategies tend to be complex and expensive. Therefore, there is interest in finding novel catalyst systems that can enhance the commercial utility of catalysts and enable the production of polymers with improved properties.

Catalysts for olefin polymerization are based on bis(phenolate) complexes as catalyst precursors, typically activated by activators containing alumoxanes or non-coordinating anions. Examples of bis(phenolate) complexes are described in the following documents:

KR2018-022137 (LG Chem.) describes transition metal complexes of bis(methylphenylphenolate)pyridine.

US 7,030,256 B2 (Symyx Technologies, Inc.) describes bridged diaromatic ligands, catalysts, polymerization processes, and polymers therefrom.

US 6,825,296 (University of Hong Kong) describes transition metal complexes of metal-coordinating bis(phenolate) ligands having two six-membered rings.

US 7,847,099 (California Institute of Technology) describes transition metal complexes of metal-coordinating bis(phenolate) ligands having two six-membered rings.

WO2016/172110 (University Technologies) describes complexes of tridentate bis(phenolate) ligands featuring acyclic ether or thioether donors.

Other references include: Baier, M. C. et al. "Post-Metallocenes in the Industrial Production of Polyolefins" Angew. Chem. Int. Ed. 2014, 53, 9722-9744; Golisz and Bercaw "Synthesis of Early Transition Metal Bisphenolate Complexes and their use as Olefin Polymerization Catalysts" Macromolecules 2009, 42, 8751-8762.

In addition, it is advantageous to carry out commercial solution polymerization reactions at elevated temperatures. Two major catalyst limitations that often prevent access to such high temperature polymerizations are catalyst efficiency and the molecular weight of the polymer produced, both of which decrease with increasing temperature. Typical metallocene catalysts suitable for use in the production of polyethylene copolymers have relatively limited molecular weight capabilities that require low process temperatures to achieve the desired low melt flow rate products.

The newly developed single-site catalysts described in related U.S. Patent Application No. 16/787,909, filed February 11, 2020, have the ability to produce high molecular weight polymers at high polymerization temperatures. These catalysts, when used in solution processes in combination with various types of activators, can produce polymer compositions with superior properties, especially lower Tm with superior molecular weight. Furthermore, the catalyst activity is high, facilitating its use in commercially relevant process conditions. The novel process provides novel polymers with an extended melt flow rate range, increasing reactor throughput and allowing production at higher polymerization temperatures during polymer production.

The present invention relates to polymer compositions comprising cyclic olefins, such as copolymers of cyclic olefins with ethylene and/or propylene and/or one or more _C4 - _C12 alpha olefins, and blends comprising such copolymers, the polymer compositions being produced in a solution process using transition metal catalyst complexes of bis(phenolate) ligands. Preferably, the bis(phenolate) ligands are dianionic tridentate ligands featuring a central neutral heterocyclic Lewis base and two phenolate donors, the tridentate ligands co-ordinated to the metal center to form two eight-membered rings. The polymer and copolymer compositions described herein preferably contain greater than 0.1 mole % of the cyclic olefin, ethylene and/or propylene, and any _C4 or higher alpha olefin comonomers.

［式中：
Ｍは、３～６族の遷移金属またはランタニドであり；
ＥおよびＥ’は、それぞれ独立して、Ｏ、ＳまたはＮＲ^９であり、ここに、Ｒ^９は、独立して、水素、Ｃ_１～Ｃ_４０ヒドロカルビル、Ｃ_１～Ｃ_４０置換ヒドロカルビルまたはヘテロ原子含有基であり；
Ｑは、金属Ｍと配位結合を形成する、１４、１５、または１６族の原子であり、
Ａ^１ＱＡ^１’は、３原子架橋により、Ａ^２とＡ^２’を連結する、４～４０個の非水素原子を含むヘテロサイクリックルイス塩基の一部であり、ここに、Ｑは、３原子架橋の中心原子であり、Ａ^１およびＡ^１’は、独立して、Ｃ、Ｎ、またはＣ（Ｒ^２２）であり、Ｒ^２２は、水素、Ｃ_１～Ｃ_２０ヒドロカルビル、Ｃ_１～Ｃ_２０置換ヒドロカルビルから選択され；

は、２原子架橋によりＡ^１とＥ結合アリール基を連結する、２～４０個の非水素原子を含む二価の基であり；

は、２原子架橋によりＡ^１’とＥ’結合アリール基を連結する、２～４０個の非水素原子を含む二価の基であり；
Ｌは、ルイス塩基であり；
Ｘは、アニオン配位子であり；
ｎは１、２または３であり；
ｍは０、１、または２であり；
ｎ＋ｍは４以下であり；
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^１’、Ｒ^２’、Ｒ^３’、およびＲ^４’は、それぞれ独立して、水素、Ｃ_１～Ｃ_４０ヒドロカルビル、Ｃ_１～Ｃ_４０置換ヒドロカルビル、ヘテロ原子、またはヘテロ原子含有基であり；
Ｒ^１とＲ^２、Ｒ^２とＲ^３、Ｒ^３とＲ^４、Ｒ^１’とＲ^２’、Ｒ^２’とＲ^３’、Ｒ^３’とＲ^４’のうちの１つまたは複数は、結合して、それぞれが５、６、７、または８個の環原子を有する、１つまたは複数の、置換ヒドロカルビル環、非置換ヒドロカルビル環、置換ヘテロサイクリック環、または非置換ヘテロサイクリック環を形成してもよく、ここに、環上の置換は、結合して追加の環を形成してもよく；
任意の２つのＬ基は、結合して、二座ルイス塩基を形成してもよく；
Ｘ基は、Ｌ基に結合して、モノアニオン性二座基を形成してもよく；
任意の２つのＸ基は、結合して、ジアニオン配位子を形成してもよい。］
により表される触媒化合物を含む触媒系と接触させることを含む、重合方法。 The present invention relates to polymer compositions, such as copolymers of cyclic olefins and ethylene and/or propylene and/or any _C4 to _C12 alpha olefin comonomers, and blends comprising such copolymers, which are prepared in a solution process using a bis(phenolate) complex, preferably a bis(phenolate) complex represented by formula (I):

[Wherein:
M is a Group 3-6 transition metal or a lanthanide;
E and E' are each independently O, S, or NR ⁹ , where R ⁹ is independently hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl, or a heteroatom-containing group;
Q is an atom of Group 14, 15, or 16 that forms a coordinate bond with the metal M;
A ¹ QA ^1′ is a portion of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms connecting A ² and A ^2′ by a three atom bridge, where Q is the central atom of the three atom bridge, A ¹ and A ^1′ are independently C, N, or C(R ²² ), and R ²² is selected from hydrogen, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ substituted hydrocarbyl;

is a divalent group containing 2 to 40 non-hydrogen atoms that connects ^A1 and the E-linked aryl group through a two atom bridge;

is a divalent group containing 2 to 40 non-hydrogen atoms that connects the A ^1′ and E′ linked aryl groups through a two atom bridge;
L is a Lewis base;
X is an anionic ligand;
n is 1, 2 or 3;
m is 0, 1, or 2;
n+m is 4 or less;
R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^2' , R ^3' , and R ^4' are each independently hydrogen, a C ₁ -C ₄₀ hydrocarbyl, a C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group;
one or more of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^1′ and R ^2′ , R ^2′ and R ^3′ , R ^3′ and R ^4′ may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, where substitutions on the rings may be joined to form additional rings;
Any two L groups may be combined to form a bidentate Lewis base;
The X group may be attached to the L group to form a monoanionic bidentate group;
Any two X groups may be combined to form a dianionic ligand.
A process for polymerization comprising contacting a catalyst compound represented by the formula:

The present invention also relates to a liquid phase process for polymerizing cyclic olefins comprising contacting a catalyst compound described herein with an activator, a cyclic olefin, and optionally ethylene and/or propylene, and one or more _C4 to _C10 alpha-olefin comonomers. The present invention further relates to a polymer composition comprising the cyclic olefin produced by the process described herein.

DEFINITIONS For purposes of the present invention and the claims, the following definitions shall be used.

The new numbering scheme for the Periodic Table Groups is that described in Chemical and Engineering News, v.63(5), pg. 27 (1985). Thus, a "Group 4 metal" is an element in Group 4 of the Periodic Table, e.g., Hf, Ti, or Zr.

"Catalyst productivity" is a measure of the mass of polymer produced using a known amount of polymerization catalyst. Typically, "catalyst productivity" is expressed in units such as kg of polymer per kg of catalyst, or grams of polymer per millimole of catalyst. If no units are specified, "catalyst productivity" is in grams of polymer per gram of catalyst. To calculate catalyst productivity, only the weight of the transition metal component of the catalyst is used (i.e., excluding activators and/or cocatalysts). "Catalyst activity" is a measure of the mass of polymer produced using a known amount of polymerization catalyst per unit time for batch and semi-batch polymerizations. Usually, "catalyst activity" is expressed in units such as (g of polymer)/(mmole of catalyst)/hour or (kg of polymer)/(mmole of catalyst)/hour. If no units are specified, "catalyst activity" is (g of polymer)/(mmole of catalyst)/hour.

"Conversion" is the percentage of monomer that is converted to polymer product in a polymerization, expressed as a percentage, and calculated based on polymer yield, polymer composition, and the amount of monomer fed to the reactor.

An "olefin" (also called an "alkene") is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. When a polymer or copolymer is referred to herein and in the appended claims as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is described as having an "ethylene" content of 35% to 55% by weight, it is understood that the mer units in the copolymer are derived from ethylene in a polymerization reaction, and the derived units are present in an amount of 35% to 55% by weight, based on the weight of the copolymer. A "polymer" has two or more of the same or different mer units. A "homopolymer" is a polymer having the same mer units. A "copolymer" is a polymer having two or more mer units that are different from each other. A "terpolymer" is a polymer having three mer units that are different from each other. Thus, the definition of copolymer as used herein includes terpolymers, etc. "Different" when used in reference to mer units indicates that the mer units differ from one another by at least one atom or are isomerically different. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer that contains at least 50 mol% ethylene-derived units, and a "propylene polymer" or "propylene copolymer" is a polymer or copolymer that contains at least 50 mol% propylene-derived units. A polyethylene composition comprises an ethylene polymer or ethylene copolymer.

Ethylene can also be considered an alpha-olefin.

Unless otherwise specified, the term " _Cn " means a hydrocarbon having n carbon atoms per molecule, where n is a positive integer.

The term "hydrocarbon" refers to a class of compounds containing hydrogen bonded to carbon and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds with different values of n. Similarly, a " _Cm - _Cy " group or compound means a group or compound containing a total number of carbon atoms ranging from m to y. Thus, a C1-C50 alkyl group means an alkyl group containing a total number of carbon atoms ranging from 1 to 50.

The terms "group," "radical," and "substituent" can be used interchangeably.

The terms "hydrocarbyl radical", "hydrocarbyl group", or "hydrocarbyl" may be used interchangeably and are defined to mean a group consisting solely of hydrogen and carbon atoms. Preferred hydrocarbyls are C ₁ -C ₁₀₀ radicals and may be linear, branched, or cyclic, and if cyclic, may be aromatic or non-aromatic. Examples of such radicals include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, octylcyclopropyl, and the like; aryl groups such as cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like; and the like, for example, phenyl, benzylnaphthalen-2-yl, and the like.

Unless otherwise specified (e.g., in the definition of "substituted hydrocarbyl"), the term "substituted" means that at least one hydrogen atom is replaced with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom or heteroatom-containing group such as a halogen (e.g., Br, Cl, F, or I), or at least one functional group such as -NR ^{* 2} , -OR ^* , -SeR*, -TeR ^* , -PR ^{* 2} , -AsR ^{* 2} , -SbR ^*2 , -SR ^* , -BR*2, -SiR* ³ , -GeR ^*3 , -SnR*3, -PbR ^*3 , -( _CH2 ) _q -SiR ^*3, etc. wherein q is 1 to 10, each R ^* is independently hydrogen, a hydrocarbyl or halocarbyl radical, and two or more R ^* may together form a substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic ring, or a polycyclic ring structure, or mean that at least one heteroatom is inserted within the hydrocarbyl ring.

The term "substituted hydrocarbyl" refers to an alkyl group in which at least one hydrogen atom of a hydrocarbyl radical has been replaced with at least one heteroatom (such as a halogen, e.g., Br, Cl, F or I) or heteroatom-containing group (such as a functional group, e.g., -NR ^*2 , -OR ^* , -SeR ^* , -TeR ^* , -PR* ² , -AsR ^{* 2} , -SbR*2, -SR ^* , -BR ^{*2 ,} -SiR ^*3 , -GeR*3, -SnR ^*3 , -PbR ^*3 , -( _CH2 ) _q -SiR ^*3 , etc., where q is 1 to 10 and each R ^* is independently hydrogen, a hydrocarbyl, or a halocarbyl radical, and two or more R ^* may be attached to form a substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic cyclic or polycyclic structure), or at least one heteroatom is inserted within the hydrocarbyl ring.

The term "aryl" or "aryl group" refers to an aromatic ring (typically consisting of six carbon atoms) and substituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Similarly, heteroaryl refers to an aryl group in which a ring carbon atom (or two or three ring carbon atoms) is replaced with a heteroatom such as N, O, or S. As used herein, it also refers to pseudoaromatic, which is a heterocyclic substituent that has similar properties and structure (nearly planar) as aromatic heterocyclic ligands, but is not aromatic by definition.

The term "substituted aromatic" means an aromatic group having one or more hydrogen radicals replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

［式中、Ｒ^１８は、水素、Ｃ_１～Ｃ_４０ヒドロカルビル（Ｃ_１～Ｃ_４０アルキルなど）またはＣ_１～Ｃ_４０置換ヒドロカルビル、ヘテロ原子またはヘテロ原子含有基であり、Ｅ^１７は、酸素、硫黄、またはＮＲ^１７であり、Ｒ^１７、Ｒ^１９、Ｒ^２０、およびＲ^２１は、それぞれお独立して、水素、Ｃ_１～Ｃ_４０ヒドロカルビル（Ｃ_１～Ｃ_４０アルキルなど）またはＣ_１～Ｃ_４０置換ヒドロカルビル、ヘテロ原子またはヘテロ原子含有基から選択され、またはＲ^１８、Ｒ^１９、Ｒ^２０、およびＲ^２１の２つ以上は、結合して、Ｃ_４～Ｃ_６２環式もしくは多環式環構造、またはそれらの組み合わせを形成し、波線は、置換フェノラート基が触媒化合物の残りの部分と結合する場所を示す。］
で表される。 A "substituted phenolate" is a phenolate group in which at least 1, 2, 3, 4, or 5 hydrogen atoms at the 2-, 3-, 4-, and ^/ or 6-positions have been replaced with at least one non-hydrogen group, e.g., a hydrocarbyl group, a ^heteroatom or a heteroatom-containing group, e.g., a halogen (such as Br, Cl, F, or I), or at least one functional group (such as -NR ^*2 , -OR*, -SeR ^* , -TeR*, -PR ^{*2 ,} -AsR ^{* 2} , -SbR ^{* 2} , -SR ^* , -BR*2, -SiR ^{*3, -GeR*3} , -SnR*3, -PbR ^*3 , -( _CH2 ) _q -SiR ^*3 , etc., where q is 1 to 10 and each R ^* is independently hydrogen, a hydrocarbyl, or a halocarbyl radical, and two or more R ^{The *} may together form a substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic or polycyclic ring structure, where the 1-position is a phenolate group (Ph-O-, Ph-S-, and Ph-N(R^)- group, where R^ is hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group. Preferably, the "substituted phenolate" group in the catalyst compounds described herein has the formula:

wherein R ¹⁸ is hydrogen, C ₁ -C ₄₀ hydrocarbyl (such as C ₁ -C ₄₀ alkyl) or C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom or a heteroatom containing group; E ¹⁷ is oxygen, sulfur, or NR ¹⁷ ; R ¹⁷ , R ¹⁹ , R ²⁰ , and R ²¹ are each independently selected from hydrogen, C ₁ -C ₄₀ hydrocarbyl (such as C ₁ -C ₄₀ alkyl) or C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom or a heteroatom containing group; or two or more of R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ are joined to form a C ₄ -C ₆₂ cyclic or polycyclic ring structure, or combinations thereof; and the wavy line indicates where the substituted phenolate group is attached to the remainder of the catalyst compound.
It is expressed as:

An "alkyl substituted phenolate" is a phenolate group in which at least 1, 2, ₃ , 4, or 5 hydrogen atoms at the 2-, 3-, 4-, and/or 6-positions are replaced with at least one alkyl group, e.g., _C1 -C40, _C2 - _C20 , or _C3 - _C12 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, octylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantanyl, and the like, or substituted analogs thereof.

An "aryl substituted phenolate" is a phenolate group in which at least 1, 2, 3, _{4, or 5 hydrogen atoms at the 2-, 3-, 4-, and/or 6-positions are replaced with at least one aryl group, e.g., C1-C40 , C2 - C20} , or C3- _C12 aryl, such as phenyl _, 4-fluorophenyl, 2-methylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, mesityl, 2-ethylphenyl, naphthalen-2-yl, and the like, or substituted analogs thereof.

The term "ring atom" means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has six ring atoms and a tetrahydrofuran group has five ring atoms.

A heterocyclic ring (also called heterocyclic) is a ring that has heteroatoms in the ring structure, as opposed to a "heteroatom-substituted ring" in which a hydrogen on a ring atom is replaced with a heteroatom. For example, tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. Substituted heterocyclic ring refers to a heterocyclic ring that has one or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

A substituted hydrocarbyl ring means a ring composed of carbon and hydrogen atoms having one or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom-containing group.

For purposes of this disclosure, with respect to catalyst compounds (e.g., substituted bis(phenolate) catalyst compounds), the term "substituted" means that a hydrogen group is replaced with at least one functional group such as a hydrocarbyl group, a heteroatom or a heteroatom-containing group, e.g., a halogen (Br, Cl, F, I, etc.) or -NR ^{* 2} , -OR ^* , -SeR ^* , -TeR ^* , -PR ^*2 , -AsR*2, SbR ^{* 2} , ^-SR *, -BR* ² , -SiR ^*3 , -GeR*3, -SnR ^*3 , -PbR ^* 3, -( _CH2 ) _q -SiR ^*3 , etc. wherein q is 1 to 10, each R ^* is independently hydrogen, a hydrocarbyl or halocarbyl group, and two or more R ^* may combine to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure, or at least one heteroatom may be inserted within the hydrocarbyl ring.

［式中、Ｒ^Ａ、Ｒ^ＢおよびＲ^Ｃは、互いに結合していてもよいヒドロカルビル基または置換ヒドロカルビル基であり、波線は、第三級ヒドロカルビル基が他の基との結合を形成する場所を示す。］
により示され得る。 A tertiary hydrocarbyl group has a carbon atom bonded to three other carbon atoms. When the hydrocarbyl group is an alkyl group, the tertiary hydrocarbyl group is also referred to as a tertiary alkyl group. Examples of tertiary hydrocarbyl groups include tert-butyl, 2-methylbutan-2-yl, 2-methylhexan-2-yl, 2-phenylpropan-2-yl, 2-cyclohexylpropan-2-yl, 1-methylcyclohexyl, 1-adamantyl, bicyclo[2.2.1]heptan-1-yl, and the like. ... the formula A:

where R ^A , R ^B and R ^C are hydrocarbyl or substituted hydrocarbyl groups which may be bonded to each other, and the wavy lines indicate where the tertiary hydrocarbyl groups form bonds to other groups.
It can be shown by:

［式中、Ｒ^Ａは、ヒドロカルビル基または置換ヒドロカルビル基であり、Ｒ^Ｄは、それぞれ独立して、水素またはヒドロカルビル基または置換ヒドロカルビル基であり、ｗは１～約３０の整数であり、Ｒ^Ａおよび１つまたは複数のＲ^Ｄ _、およびまたは２つ以上のＲ^Ｄは、任意に互いに結合して追加の環を形成してもよい。］
により示され得る。 A cyclic tertiary hydrocarbyl group is defined as a tertiary hydrocarbyl group which forms at least one alicyclic (non-aromatic) ring. Cyclic tertiary hydrocarbyl groups are also referred to as alicyclic tertiary hydrocarbyl groups. When the hydrocarbyl group is an alkyl group, the cyclic tertiary hydrocarbyl group is also referred to as a cyclic tertiary alkyl group or an alicyclic tertiary alkyl group. Examples of cyclic tertiary hydrocarbyl groups include 1-adamantanyl, 1-methylcyclohexyl, 1-methylcyclopentyl, 1-methylcyclooctyl, 1-methylcyclodecyl, 1-methylcyclododecyl, bicyclo[3.3.1]nonan-1-yl, bicyclo[2.2.1]heptan-1-yl, bicyclo[2.3.3]hexan-1-yl, bicyclo[1.1.1]pentan-1-yl, bicyclo[2.2.2]octan-1-yl, and the like. Cyclic tertiary hydrocarbyl groups are represented by formula B:

wherein R ^A is a hydrocarbyl group or a substituted hydrocarbyl group, each R ^D is independently hydrogen or a hydrocarbyl group or a substituted hydrocarbyl group, w is an integer from 1 to about 30, and R ^A and one or more R ^D _, and/or two or more R ^D may optionally be joined together to form additional rings.
It can be shown by:

If the cyclic tertiary hydrocarbyl group contains two or more alicyclic rings, it may be referred to as a polycyclic tertiary hydrocarbyl group, and if the hydrocarbyl group is an alkyl group, it may be referred to as a polycyclic tertiary alkyl group.

The terms "alkyl radical" and "alkyl" are used interchangeably throughout this disclosure. For the purposes of this disclosure, an "alkyl radical" is defined to be a C ₁ -C ₁₀₀ alkyl, which may be straight-chained, branched, or cyclic. Examples of such radicals include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, octylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and substituted analogs thereof. A substituted alkyl radical is one in which at least one hydrogen atom of the alkyl radical is replaced with at least one non-hydrogen atom, e.g., a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, e.g., a halogen (Br, Cl, F or I) or at least one functional group, e.g., -NR ^*2 , -OR ^* , -SeR ^* , ^{-TeR *} , -PR ^*2 , -AsR ^*2 , -SbR*2, -SR ^* , -BR ^*2 , -SiR ^*3 , -GeR ^{* 3} , -SnR*3, -PbR ^*3 , -( _CH2 )q-SiR ^*3 , and the like. wherein q is 1 to 10, each R ^* is independently hydrogen, a hydrocarbyl or halocarbyl group, and two or more R ^* may combine to form a substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic ring or polycyclic structure, or at least one heteroatom may be inserted within the hydrocarbyl ring.

When isomers of a specified alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), a reference to one member of the group (e.g., n-butyl) explicitly discloses the remaining isomers within the family (e.g., isobutyl, sec-butyl, and tert-butyl). Similarly, a reference to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) explicitly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl).

As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, Mz is z-average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are in g/mol (gmol- ¹ ).

The following abbreviations may be used herein: Me is methyl, Et is ethyl, Pr is propyl, cPr is cyclopropyl, nPr is n-propyl, iPr is isopropyl, Bu is butyl, nBu is normal butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, Oct is octyl, Ph is phenyl, MAO is methylalumoxane, dme (also called DME) is 1,2-dimethoxyethane, p-tBu is para-tert-butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOA and TNOAL are tri(n-octyl)aluminum, p-Me is para-methyl, Bn is benzyl (i.e., CH ₂ Ph is tetrahydrofuran, THF (also called thf) is tetrahydrofuran, RT is room temperature (23° C. unless otherwise specified), tol is toluene, EtOAc is ethyl acetate, Cbz is carbazole, Cy is cyclohexyl, cP is cyclopentene, NB is 2-norbornene, h is hours, and min is minutes. Micromole may be abbreviated as umol or μmol. Microliter may be abbreviated as uL or μL.

A "catalyst system" is a combination that includes at least one catalyst compound and at least one activator. When "catalyst system" is used to describe such a pair prior to activation, it means the unactivated catalyst complex (pre-catalyst) together with the activator and optionally a co-activator. When used to describe such a pair after activation, it means the activated complex and the activator or other charge-balancing moiety. The transition metal compound can be neutral, as in a pre-catalyst, or a charged species with a counterion, as in an activated catalyst system. For purposes of the present invention and claims, when a catalyst system is described as including the neutral stable form of a component, it is well understood by those skilled in the art that the ionic form of the component is the form that reacts with a monomer to produce a polymer. A polymerization catalyst system is a catalyst system that is capable of polymerizing a monomer into a polymer.

In the description herein, the catalyst may be described as a catalyst, a catalyst precursor, a pre-catalyst compound, a catalyst compound or a transition metal compound, and these terms are used interchangeably.

An "anionic ligand" is a negatively charged ligand that donates one or more electron pairs to a metal ion. The term "anionic donor" is used interchangeably with "anionic ligand." Examples of anion donors in the context of the present invention include, but are not limited to, methyl, chloride, fluoride, alkoxide, aryloxide, alkyl, alkenyl, thiolate, carboxylate, amide, methyl, benzyl, hydride, amidinate, amidate, and phenyl. Two anion donors may combine to form a dianionic group.

A "neutral Lewis base" or "neutral donor group" is an uncharged (i.e., neutral) group that donates one or more electron pairs to a metal ion. Non-limiting examples of neutral Lewis bases include ethers, thioethers, amines, phosphines, ethyl ethers, tetrahydrofuran, dimethylsulfide, triethylamine, pyridine, alkenes, alkynes, arenes, and carbenes. Lewis bases may combine to form bidentate or tridentate Lewis bases.

For purposes of this invention and the claims thereto, phenolate donors include Ph-O-, Ph-S-, and Ph-N(R^)- groups, where R^ is hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, and Ph is an optionally substituted phenyl.

DETAILED DESCRIPTION The present invention relates to polymer compositions containing cyclic monomers prepared using a solution process and a novel family of catalysts including transition metal complexes of dianionic tridentate ligands that feature a bis(phenolate) ligand, preferably a central neutral donor group and two phenolate donors, where the tridentate ligand coordinates to the metal center to form two eight-membered rings. In this type of complex, it is advantageous for the central neutral donor to be a heterocyclic group. It is particularly advantageous for the heterocyclic group to lack a hydrogen in the alpha position to the heteroatom. It is also advantageous for this type of complex to have the phenolate substituted with one or more cyclic tertiary alkyl substituents. The use of cyclic tertiary alkyl substituted phenolates is demonstrated to improve the ability of these catalysts to produce high molecular weight polymers.

Complexes of substituted bis(phenolate) ligands (e.g., adamantanyl-substituted bis(phenolate) ligands) useful herein, when combined with a non-coordinating anion or an activator such as an alumoxane activator, form active olefin polymerization catalysts. Useful bis(arylphenolate)pyridine complexes include tridentate bis(arylphenolate)pyridine ligands coordinated to a Group 4 transition metal forming two eight-membered rings.

The present invention also relates to a solution process for producing a polymer composition comprising a cyclic monomer utilizing a metal complex comprising a metal selected from Groups 3-6 or Lanthanide metals and a tridentate dianionic ligand comprising two anionic donor groups and a neutral Lewis base donor, wherein the neutral Lewis base donor is covalently bonded between the two anionic donors and the metal-ligand complex is characterized by a pair of eight-membered metallocyclic rings.

The present invention relates to a catalyst system for use in a solution process for preparing a cyclic monomer-containing polymer composition comprising an activator and one or more catalyst compounds described herein.

The present invention also relates to a solution process for polymerizing olefins (preferably at higher temperatures) using the catalyst compounds described herein, which comprises contacting a cyclic monomer and, optionally, one or more olefin comonomers with a catalyst system comprising an activator and catalyst compound described herein.

The present disclosure also relates to catalyst systems comprising the transition metal compounds and activator compounds described herein, activators for activating the transition metal compounds in catalyst systems for polymerizing cyclic monomers and, optionally, one or more olefin comonomers, and methods of polymerizing the olefins, the methods comprising contacting one or more olefin comonomers with a catalyst system comprising a transition metal compound and an activator compound under polymerization conditions, wherein no aromatic solvent such as toluene is present (e.g., present at zero mole % or present at less than 1 mole % relative to the moles of activator, and preferably the catalyst system, the polymerization reaction and/or the polymer produced does not contain detectable aromatic hydrocarbon solvents such as toluene).

The cyclic olefin-containing polymer compositions produced herein preferably contain 0 ppm (alternatively less than 1 ppm, alternatively less than 100 ppm, alternatively less than 500 ppm) of aromatic hydrocarbons such as toluene. Preferably, the polyethylene compositions produced herein contain 0 ppm (alternatively less than 1 ppm) of toluene.

The catalyst system used herein preferably contains 0 ppm (alternatively less than 1 ppm) of aromatic hydrocarbons. Preferably, the catalyst system used herein contains 0 ppm (alternatively less than 1 ppm) of toluene.

CATALYST COMPOUNDS The terms "catalyst,""compound,""catalystcompound," and "complex" can be used interchangeably to refer to transition metal or lanthanide metal complexes that, when combined with an appropriate activator, form olefin polymerization catalysts.

The catalyst complexes of the present invention comprise a metal or lanthanide metal selected from Groups 3, 4, 5, or 6 of the Periodic Table of the Elements, a tridentate dianionic ligand comprising two anion donor groups, and a neutral heterocyclic Lewis base donor, where the heterocyclic donor is covalently bonded between the two anionic donors. Preferably, the catalyst complexes comprise a dianionic tridentate ligand featuring a central heterocyclic donor group and two phenolate donors, where the tridentate ligand coordinates to the metal center to form two eight-membered rings. Also preferably, the catalyst complexes comprise a tridentate dianionic ligand featuring a central heterocyclic donor bonded to two phenolate donors, where the central heterocyclic ring is linked to each phenolate donor by a 1,2-arylene bridge (e.g., 1,2-phenylene).

The metal is preferably selected from Group 3, 4, 5, or 6 elements. Preferably, metal M is a Group 4 metal. Most preferably, metal M is zirconium or hafnium.

Preferably, the heterocyclic Lewis base donor features a nitrogen or oxygen donor atom. Preferred heterocyclic ring groups include derivatives of pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, and substituted variants thereof. Preferably, the heterocyclic Lewis base lacks a hydrogen alpha to the donor atom. Particularly preferred heterocyclic Lewis base donors include pyridine, 3-substituted pyridine, and 4-substituted pyridine.

The anion donor of the tridentate dianionic ligand may be an aryl thiolate, phenolate, or anilide. The preferred anion donor is phenolate. It is preferred that the tridentate dianionic ligand coordinates to the metal center to form a complex that lacks a mirror plane of symmetry. It is preferred that the tridentate dianionic ligand coordinates to the metal center to form a complex that has a twofold axis of symmetry. When determining the symmetry of a bis(phenolate) complex, only the metal and the dianionic tridentate ligand are considered (i.e., the remaining ligands are ignored).

Bis(phenolate) ligands useful in the present invention include dianionic polydentate (e.g., bidentate, tridentate, or tetradentate) ligands featuring two anionic phenolate donors. Preferably, the bis(phenolate) ligand is a tridentate dianionic ligand that coordinates to the metal M such that a pair of eight-membered metallocyclic rings are formed. Preferred bis(phenolate) ligands wrap around the metal to form a complex with a two-fold axis, thus giving the complex _C2 symmetry. The _C2 geometry and the eight-membered metallocyclic ring are characteristics of these complexes that make them effective catalyst components for the production of polyolefins, particularly isotactic poly(alphaolefins). If the ligand is coordinated to the metal such that the complex has mirror plane ( _Cs ) symmetry, the catalyst is expected to produce only atactic poly(alphaolefins). These symmetric reactivity rules are summarized in Macromolecules 2009, v.42, pp. 8751-8762 by Bercaw. The pair of 8-membered metallocyclic rings of the complexes of the present invention is also a notable feature that favors catalytic activity, temperature stability, and equiselectivity of monomer binding. It is known that related Group 4 complexes, featuring smaller 6-membered metallocyclic rings, form mixtures of _C2 and _Cs symmetric complexes when used in the polymerization of olefins, and thus are less suitable for the production of highly isotactic poly(alpha-olefins) (Macromolecules 2009, v.42, pp. 8751-8762).

The bis(phenolate) ligands of the present invention containing an oxygen donor group (i.e., E=E'=oxygen in formula (I)) are preferably substituted with alkyl, substituted alkyl, aryl, or other groups. Advantageously, each phenolate group is substituted at a ring position adjacent to the oxygen donor atom. The substitution at the position adjacent to the oxygen donor atom is preferably an alkyl group having 1 to 20 carbon atoms. The substitution at the position adjacent to the oxygen donor atom is preferably a non-aromatic cyclic alkyl group having one or more 5- or 6-membered rings. The substitution at the position adjacent to the oxygen donor atom is preferably a cyclic tertiary alkyl group. It is highly preferred that the substitution at the position adjacent to the oxygen donor atom is adamantan-1-yl or substituted adamantan-1-yl.

The neutral heterocyclic Lewis base donor is covalently bonded between the two anionic donors via a "linker group" that connects the heterocyclic Lewis base to the phenolate group. The "linker group" is shown as (A ³ A ² ) and (A ^2' A ^3' ) in formula (I). The selection of each linker group can affect the performance of the catalyst, including the stereoregularity of the poly(alpha olefin) produced. Each linker group is typically a C ₂ -C ₄₀ divalent group that is two atoms in length. One or both linker groups can independently be phenylene, substituted phenylene, heteroaryl, vinylene, or an acyclic two-carbon long linker group. When one or both linker groups are phenylene, the alkyl substituents on the phenylene group can be selected to optimize the catalyst performance. Typically, one or both phenylene groups may be unsubstituted or substituted with a C 1 -C 10 alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl _, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, e.g., isopropyl, or an _isomer thereof.

［式中：
Ｍは、３、４、５、または６族の遷移金属またはランタニド（例えば、Ｈｆ、Ｚｒ、またはＴｉ）であり；
ＥおよびＥ’は、それぞれ独立して、Ｏ、ＳまたはＮＲ^９であり、ここに、Ｒ^９は、独立して、水素、Ｃ_１～Ｃ_４０ヒドロカルビル、Ｃ_１～Ｃ_４０置換ヒドロカルビルまたはヘテロ原子含有基、好ましくはＯであり、好ましくは両方のＥおよびＥ’はＯであり；
Ｑは、金属Ｍと配位結合を形成する、１４、１５、または１６族の原子であり、好ましくは、ＱはＣ、Ｏ、ＳまたはＮであり、より好ましくは、ＱはＣ、ＮまたはＯであり、最も好ましくは、ＱはＮであり；
Ａ^１ＱＡ^１’は、３原子架橋により、Ａ^２とＡ^２’を連結する、４～４０個の非水素原子を含むヘテロサイクリックルイス塩基の一部であり、ここに、Ｑは、３原子架橋の中心原子であり、（Ａ^１ＱＡ^１’は、Ａ^１とＡ^１’を結ぶ曲線で結合して、ヘテロサイクリックルイス塩基を表す）、Ａ^１およびＡ^１’は、独立して、Ｃ、Ｎ、またはＣ（Ｒ^２２）であり、Ｒ^２２は、水素、Ｃ_１～Ｃ_２０ヒドロカルビル、Ｃ_１～Ｃ_２０置換ヒドロカルビルから選択され、好ましくは、Ａ^１およびＡ^１’はＣであり；

は、２原子架橋によりＡ^１とＥ結合アリール基を連結する、２～４０個の非水素原子を含む二価の基、例えば、オルトフェニレン、置換オルトフェニレン、オルトアレーン、インドレン、置換インドレン、ベンゾチオフェン、置換ベンゾチオフェン、ピロレン、置換ピロレン、チオフェン、置換チオフェン、１，２－エチレン（－ＣＨ_２ＣＨ_２－）、置換１，２－エチレン、１，２－ビニレン（－ＨＣ＝ＣＨ－）、または置換１，２－ビニレンであり、好ましくは

は、二価のヒドロカルビル基であり；

は、２原子架橋によりＡ^１’とＥ’結合アリール基を連結する、２～４０個の非水素原子を含む二価の基、例えば、オルトフェニレン、置換オルトフェニレン、オルトアレーン、インドレン、置換インドレン、ベンゾチオフェン、置換ベンゾチオフェン、ピロレン、置換ピロレン、チオフェン、置換チオフェン、１，２－エチレン（－ＣＨ_２ＣＨ_２－）、置換１，２－エチレン、１，２－ビニレン（－ＨＣ＝ＣＨ－）、または置換１，２－ビニレンであり、好ましくは

は、二価のヒドロカルビル基であり；
Ｌは、それぞれ独立して、ルイス塩基であり；
Ｘは、それぞれ独立して、アニオン配位子であり；
ｎは１、２または３であり；
ｍは０、１、または２であり；
ｎ＋ｍは４以下であり；
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^１’、Ｒ^２’、Ｒ^３’、およびＲ^４’は、それぞれ独立して、水素、Ｃ_１～Ｃ_４０ヒドロカルビル、Ｃ_１～Ｃ_４０置換ヒドロカルビル、ヘテロ原子、またはヘテロ原子含有基であり（好ましくは、Ｒ^１’およびＲ^１は、独立して環状第三級アルキル基などの環状基である）；
Ｒ^１とＲ^２、Ｒ^２とＲ^３、Ｒ^３とＲ^４、Ｒ^１’とＲ^２’、Ｒ^２’とＲ^３’、Ｒ^３’とＲ^４’のうちの１つまたは複数は、結合して、それぞれが５、６、７、または８個の環原子を有する、１つまたは複数の、置換ヒドロカルビル環、非置換ヒドロカルビル環、置換ヘテロサイクリック環、または非置換ヘテロサイクリック環を形成してもよく、ここに、環上の置換は、結合して追加の環を形成してもよく；
任意の２つのＬ基は、結合して、二座ルイス塩基を形成してもよく；
Ｘ基は、Ｌ基に結合して、モノアニオン性二座基を形成してもよく；
任意の２つのＸ基は、結合して、ジアニオン配位子を形成してもよい。］ The present invention further relates to catalyst compounds of formula (I) and catalyst systems comprising such compounds.

[Wherein:
M is a Group 3, 4, 5, or 6 transition metal or lanthanide (e.g., Hf, Zr, or Ti);
E and E' are each independently O, S or NR ⁹ , where R ⁹ is independently hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl or a heteroatom containing group, preferably O, and preferably both E and E' are O;
Q is an atom of Group 14, 15, or 16 that forms a coordinate bond with the metal M, preferably Q is C, O, S, or N, more preferably Q is C, N, or O, and most preferably Q is N;
A ¹ QA ^{1 '} is a portion of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms linking A ² and A ^{2 '} by a 3 atom bridge, where Q is the central atom of the 3 atom bridge, (A ¹ QA ^{1 '} is joined by a curved line connecting A ¹ and A ^{1 '} to represent the heterocyclic Lewis base), A ¹ and A ^{1 '} are independently C, N, or C (R ²² ), R ²² is selected from hydrogen, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ substituted hydrocarbyl, preferably A ¹ and A ^{1 '} are C;

is a divalent group containing 2 to 40 non-hydrogen atoms linking ^A1 and the E-linked aryl group by a two-atom bridge, such as orthophenylene, substituted orthophenylene, orthoarene, indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, substituted thiophene, 1,2-ethylene ( _-CH2CH2- ), substituted 1,2 _- ethylene, 1,2-vinylene (-HC=CH-), or substituted 1,2-vinylene, preferably

is a divalent hydrocarbyl group;

is a divalent group containing 2 to 40 non-hydrogen atoms linking the A ^1′ and E′ linked aryl groups by a two atom bridge, e.g., orthophenylene, substituted orthophenylene, orthoarene, indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, substituted thiophene, 1,2-ethylene (—CH ₂ CH ₂ —), substituted 1,2-ethylene, 1,2-vinylene (—HC═CH—), or substituted 1,2-vinylene, preferably

is a divalent hydrocarbyl group;
Each L is independently a Lewis base;
Each X is independently an anionic ligand;
n is 1, 2 or 3;
m is 0, 1, or 2;
n+m is 4 or less;
R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^2' , R ^3' , and R ^4' are each independently hydrogen, a C ₁ -C ₄₀ hydrocarbyl, a C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group (preferably, R ^1' and R ¹ are independently a cyclic group such as a cyclic tertiary alkyl group);
one or more of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^1′ and R ^2′ , R ^2′ and R ^3′ , R ^3′ and R ^4′ may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, where substitutions on the rings may be joined to form additional rings;
Any two L groups may be combined to form a bidentate Lewis base;
The X group may be attached to the L group to form a monoanionic bidentate group;
Any two X groups may be combined to form a dianionic ligand.

［式中：
Ｍは、３、４、５、または６族の遷移金属またはランタニド（例えば、Ｈｆ、Ｚｒ、またはＴｉ）であり；
ＥおよびＥ’は、それぞれ独立して、Ｏ、ＳまたはＮＲ^９であり、ここに、Ｒ^９は、独立して、水素、Ｃ_１～Ｃ_４０ヒドロカルビル、Ｃ_１～Ｃ_４０置換ヒドロカルビルまたはヘテロ原子含有基であり、好ましくはＯであり、好ましくは両方のＥおよびＥ’はＯであり；
Ｌは、それぞれ独立して、ルイス塩基であり；
ｎは１、２または３であり；
ｍは０、１、または２であり；
ｎ＋ｍは４以下であり；
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^１’、Ｒ^２’、Ｒ^３’、およびＲ^４’は、それぞれ独立して、水素、Ｃ_１～Ｃ_４０ヒドロカルビル、Ｃ_１～Ｃ_４０置換ヒドロカルビル、ヘテロ原子、またはヘテロ原子含有基であり；
Ｒ^１とＲ^２、Ｒ^２とＲ^３、Ｒ^３とＲ^４、Ｒ^１’とＲ^２’、Ｒ^２’とＲ^３’、Ｒ^３’とＲ^４’の１つまたは複数は、結合して、それぞれが５、６、７、または８個の環原子を有する、１つまたは複数の、置換ヒドロカルビル環、非置換ヒドロカルビル環、置換ヘテロサイクリック環、または非置換ヘテロサイクリック環を形成してもよく、ここに、環上の置換は、結合して追加の環を形成してもよく；
任意の２つのＬ基は、結合して、二座ルイス塩基を形成してもよく；
Ｘ基は、Ｌ基に結合して、モノアニオン性二座基を形成してもよく；
任意の２つのＸ基は、結合して、ジアニオン配位子を形成してもよく；
Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^５’、Ｒ^６’、Ｒ^７’、Ｒ^８’、Ｒ^１０、Ｒ^１１、およびＲ^１２は、それぞれ独立して、水素、Ｃ_１～Ｃ_４０ヒドロカルビル、Ｃ_１～Ｃ_４０置換ヒドロカルビル、ヘテロ原子またはヘテロ原子含有基であり；
Ｒ^５とＲ^６、Ｒ^６とＲ^７、Ｒ^７とＲ^８、Ｒ^５’とＲ^６’、Ｒ^６’とＲ^７’、Ｒ^７’とＲ^８’、Ｒ^１０とＲ^１１、またはＲ^１１とＲ^１２の１つまたは複数は、結合して、それぞれが５、６、７、または８個の環原子を有する、１つまたは複数の、置換ヒドロカルビル環、非置換ヒドロカルビル環、置換ヘテロサイクリック環、または非置換ヘテロサイクリック環を形成してもよく、ここに、環上の置換は、結合して追加の環を形成してもよい。］ The present invention further relates to catalyst compounds and catalyst systems comprising such compounds, represented by formula (II):

[Wherein:
M is a Group 3, 4, 5, or 6 transition metal or lanthanide (e.g., Hf, Zr, or Ti);
E and E' are each independently O, S or NR ⁹ , where R ⁹ is independently hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl or a heteroatom containing group, preferably O, and preferably both E and E' are O;
Each L is independently a Lewis base;
n is 1, 2 or 3;
m is 0, 1, or 2;
n+m is 4 or less;
R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^2' , R ^3' , and R ^4' are each independently hydrogen, a C ₁ -C ₄₀ hydrocarbyl, a C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group;
one or more of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^1′ and R ^2′ , R ^2′ and R ^3′ , R ^3′ and R ^4′ may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, where substitutions on the rings may be joined to form additional rings;
Any two L groups may be combined to form a bidentate Lewis base;
The X group may be attached to the L group to form a monoanionic bidentate group;
Any two X groups may be combined to form a dianionic ligand;
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^5' , R ^6' , R ^7' , R ^8' , R ¹⁰ , R ¹¹ , and R ¹² are each independently hydrogen, a C ₁ -C ₄₀ hydrocarbyl, a C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group;
One or more ^{of R5} and ^R6 , ^R6 and ^R7 , ^R7 and ^R8 , R5 ^' and R6 ^' , R6 ^' and ^R7' , R7 ^' and R8 ^' , ^R10 and ^R11 , or ^R11 and ^R12 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, where substitutions on the rings may be joined to form additional rings.

The metal M is preferably selected from elements of Groups 3, 4, 5, or 6, more preferably from Group 4. Most preferably, the metal M is zirconium or hafnium.

The donor atom Q of the neutral heterocyclic Lewis base (in formula (I)) is preferably nitrogen, carbon, or oxygen. A preferred Q is nitrogen.

Non-limiting examples of neutral heterocyclic Lewis base groups include derivatives of pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, and substituted variants thereof. Preferred heterocyclic Lewis base groups include derivatives of pyridine, pyrazine, thiazole, and imidazole.

A ¹ and A ^1' of the heterocyclic Lewis base (in formula I) are each independently C, N, or C(R ²² ), with R ²² selected from hydrogen, C ₁ -C ₂₀ hydrocarbyl, and C ₁ -C ₂₀ substituted hydrocarbyl. Preferably, A ¹ and A ^1' are carbon. When Q is carbon, it is preferred that A ¹ and A ^1' are selected from nitrogen and C(R ²² ). When Q is nitrogen, it is preferred that A ¹ and A ^1' are carbon. It is preferred that Q=nitrogen, and A ¹ =A ^1' =carbon. When Q is nitrogen or oxygen, it is preferred that the heterocyclic Lewis base in formula (I) does not have a hydrogen atom bonded to the A ¹ or A ^1' atom. This is because it is believed that hydrogen at these positions may undergo undesirable decomposition reactions that reduce the stability of the catalytically active species.

The heterocyclic Lewis base represented by A ¹ QA ^1′ in combination with the curve connecting A ¹ and A ^1′ (in formula (I)) is preferably selected from the following, where each R ²³ group is selected from hydrogen, a heteroatom, a C ₁ -C ₂₀ alkyl, a C ₁ -C ₂₀ alkoxide, a C ₁ -C ₂₀ amide, and a C ₁ -C ₂₀ substituted alkyl.

In formula (I) or (II), E and E' are each selected from oxygen or NR ⁹ , where R ⁹ is independently hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl, or a heteroatom containing group. E and E' are preferably oxygen. When E and/or E' are NR ⁹ , R ⁹ is preferably selected from C ₁ -C ₂₀ hydrocarbyl, alkyl, or aryl. In one embodiment, E and E' are each selected from O, S, or N(alkyl) or N(aryl), where alkyl is preferably C ₁ -C 20 alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl _, undecyl, dodecyl, and the like, and aryl is a C ₆ -C ₄₀ aryl group, such as phenyl, naphthalen-2-yl, benzyl, methylphenyl, and the like.

は、独立して、Ｃ_１～Ｃ_１２ヒドロカルビル基などの二価ヒドロカルビル基である。 In an embodiment,

is independently a divalent hydrocarbyl group, such as a C ₁ to C ₁₂ hydrocarbyl group.

In the complexes represented by formula (I) or (II), when E and E' are oxygen, it is advantageous for each phenolate group to be substituted at the position adjacent to the oxygen atom (i.e., R ¹ and R ^1' in formula (I) or (II)). Thus, when E and E' are oxygen, it is preferred that each of R ¹ and R ^1' is independently a C ₁ -C ₄₀ hydrocarbyl, a C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom or a heteroatom-containing group. More preferably, R ¹ and R ^1' are each independently a non-aromatic cyclic alkyl group having one or more 5- or 6-membered rings (e.g., cyclohexyl, cyclooctyl, adamantanyl, or 1-methylcyclohexyl, or substituted adamantanyl), and most preferably a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantanyl, or substituted adamantanyl).

In some embodiments of the present invention of formula (I) or (II), R ¹ and R ^{1' are each independently a tertiary hydrocarbyl group. In other embodiments of the present invention of formula (I) or (II), R 1} and R ^{1 '} are each independently a cyclic tertiary hydrocarbyl group. In other embodiments of the present invention of formula (I) or (II), R ¹ and R ^1' are each independently a polycyclic tertiary hydrocarbyl group.

In some embodiments of the present invention of formula (I) or (II), R ¹ and R ^{1' are each independently a tertiary hydrocarbyl group. In other embodiments of the present invention of formula (I) or (II), R 1} and R ^{1 '} are each independently a cyclic tertiary hydrocarbyl group. In other embodiments of the present invention of formula (I) or (II), R ¹ and R ^1' are each independently a polycyclic tertiary hydrocarbyl group.

は、それぞれ、好ましくはオルトフェニレン基、好ましくは置換オルトフェニレン基の一部である。式（ＩＩ）のＲ^７およびＲ^７’位が水素、またはメチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル、ノナデシル、エイコシル、またはイソプロピルなどのその異性体などのＣ_１～Ｃ_２０アルキルであることが好ましい。高い立体規則性を持つポリマーをターゲットとする用途では、式（ＩＩ）のＲ^７およびＲ^７’位がＣ_１～Ｃ_２０アルキルであることが好ましい。Ｒ^７およびＲ^７’の両方がＣ_１～Ｃ_３アルキルであることが最も好ましい。 Linker group (i.e., the group shown below in formula (I))

are each preferably part of an ortho-phenylene group, preferably a substituted ortho-phenylene group. It is preferred that the R ⁷ and R ^7' positions of formula (II) are hydrogen or a C 1 -C 20 alkyl such as methyl _, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl _, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, or an isomer thereof such as isopropyl. For applications targeting polymers with high stereoregularity, it is preferred that the R ⁷ and R ⁷ ' positions of formula (II) are C ₁ -C ₂₀ alkyl. It is most preferred that both R ⁷ and R ^7' are C ₁ -C ₃ alkyl.

In embodiments of formula (I) herein, Q is C, N or O, preferably Q is N.

In an embodiment of formula (I) herein, A ¹ and A ^1' are independently carbon, nitrogen, or C(R ²² ), where R ²² is selected from hydrogen, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ substituted hydrocarbyl. Preferably, A ¹ and A ^1' are carbon.

In an embodiment of formula (I) herein, A ¹ QA ^1′ of formula (I) is a moiety of a heterocyclic Lewis base such as pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, or substituted variants thereof.

In an embodiment of formula (I) herein, A ¹ QA ^{1 '} is part of a heterocyclic Lewis base containing 2-20 non-hydrogen atoms linking A ² and A ^{2 '} by a 3 atom bridge, and Q is the central atom of the 3 atom bridge. Preferably, each A ¹ and A ^{1 '} is a carbon atom, and the A ¹ QA ^{1 '} fragment forms part of a pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, or substituted variants thereof, or substituted variants thereof.

In one embodiment of formula (I) herein, Q is carbon and each A ¹ and A ^1' is N or C(R ²² ), where R ²² is selected from hydrogen, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ substituted hydrocarbyl, a heteroatom or a heteroatom containing group. In this embodiment, the A ¹ QA ^1' fragment forms a cyclic carbene, an N-heterocyclic carbene, a cyclic aminoalkylcarbene, or a substituted variant of that group, or a part of a substituted variant thereof.

は、２～２０個の非水素原子を含む二価基であり、２原子架橋によりＡ^１をＥ結合アリール基に結合する。

は、直鎖アルキル基であるか、または環状基（例えば、置換されていてもよいオルト－フェニレン基、またはオルト－アリーレン基）またはその置換変異体の一部を形成する。 In an embodiment of formula (I) of the specification,

is a divalent group containing 2 to 20 non-hydrogen atoms, which connects ^A1 to the E-linked aryl group by a two atom bridge.

is a straight chain alkyl group or forms part of a cyclic group (eg, an optionally substituted ortho-phenylene group, or an ortho-arylene group) or substituted variants thereof.

は、２～２０個の非水素原子を含む二価の基であり、２原子架橋によりＡ^１’をＥ’結合アリール基に結合する。

は、直鎖アルキルであるか、環状基（例えば、置換されていてもよいオルト－フェニレン基、またはオルト－アリーレン基）、またはその置換変異体の一部を形成する。

is a divalent group containing 2 to 20 non-hydrogen atoms, which connects A ^1′ to the E′ linked aryl group by a two atom bridge.

is a straight chain alkyl or forms part of a cyclic group (eg, an optionally substituted ortho-phenylene or ortho-arylene group), or substituted variants thereof.

In an embodiment of the present invention, in formula (I) or (II), M is a Group 4 metal, such as Hf or Zr.

In an embodiment of the present invention, in formulas (I) and (II), E and E' are O.

In an embodiment of the invention, in formula (I) and (II), R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^2' , R ^3' , and R ^4' are independently hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl, heteroatoms or heteroatom-containing groups, or R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^1' and R 2 ^' , R ^2' and R ^3' , R ^3' and R ^4' may join to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings having 5, 6, 7 or 8 ring atoms, respectively, where substitutions on a ring, when joined to form an additional ring, may preferably be hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or isomers thereof.

In an embodiment of the present invention, in formula (I) and (II), R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^2' , R ^3' , R ^4' _and R ⁹ are selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl, dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthalen-2-yl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.

In an embodiment of the present invention, in formula (I) and (II), R ⁴ and R ^4′ are independently hydrogen or C ₁ to C ₃ hydrocarbyl, such as methyl, ethyl or propyl.

In an embodiment of the invention herein, in formula (I) and (II), R ⁹ is hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl, or a heteroatom-containing group, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof. R ⁹ is preferably methyl, ethyl, propyl, butyl, C ₁ -C ₆ alkyl, phenyl, 2-methylphenyl, 2,6-dimethylphenyl, or 2,4,6-trimethylphenyl.

In an embodiment of the invention, in formulae (I) and (II), X is each independently selected from a hydrocarbyl group having 1 to 20 carbon atoms (e.g., alkyl or aryl), a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halide, an alkylsulfonate, and combinations thereof (two or more X may form part of a fused ring or ring system). X is preferably each independently selected from a halide, an aryl, and a _C1 - _C5 alkyl group. X is preferably each independently a hydride, dimethylamide, diethylamide, methyltrimethylsilyl, neopentyl, phenyl, benzyl, methyl, ethyl, propyl, butyl, pentyl, fluoro, iodo, bromo, or chloro group.

Alternatively, each X may independently be a halide, a hydride, an alkyl group, an alkenyl group, or an arylalkyl group.

In an embodiment of the invention, in formulas (I) and (II), L is each independently a Lewis base selected from the group consisting of ethers, thioethers, amines, nitriles, imines, pyridines, halocarbons, and phosphines, preferably ethers and thioethers, and combinations thereof, and optionally two or more L may form part of a fused ring or ring system, L is preferably each independently selected from ether and thioether groups, and L is preferably each ethyl ether, tetrahydrofuran, dibutyl ether, or dimethyl sulfide group.

In an embodiment of the invention herein, in formula (I) and (II), R ¹ and R ^1' are independently a cyclic tertiary alkyl group.

In an embodiment of the invention, in formulas (I) and (II), n is 1, 2 or 3, typically 2.

In an embodiment of the present invention, in formulas (I) and (II), m is 0, 1 or 2, typically 0.

In an embodiment of the invention, in formulae (I) and (II), R ¹ and R ^1' are not hydrogen.

In an embodiment of the invention, in formula (I) and (II), M is Hf or Zr, E and E' are O; R ¹ and R ^1' are each independently C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom or a heteroatom containing group, R ² , R ³ , R ⁴ , R ^2' , R ^3' and R ^4' are each independently hydrogen, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ substituted hydrocarbyl, a heteroatom or a heteroatom containing group, or R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^1' and R ^2' , R ^2' and R ^3' , R ^3' and R One or more of ^4' may be joined to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, or substituted or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, or the substituents on the rings may be joined to form additional rings. Each X is independently selected from the group consisting of a hydrocarbyl radical having 1 to 20 carbon atoms (e.g., alkyl or aryl), a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halide, and combinations thereof (two or more X may form part of a fused ring or ring system); each L is independently selected from the group consisting of an ether, a thioether, and a halocarbon (two or more L may form part of a fused ring or ring system).

In an embodiment of the invention herein, in formula (II), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^5' , R ^6' , R ^7' , R ^8' _, R ¹⁰ , R ¹¹ and R ¹² are each independently hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or one or more adjacent R groups may combine to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and in which substitutions on the rings may be combined to form additional rings.

In an embodiment of the invention herein, in formula (II), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^5' , R ^6' , R ^7' , R ^8' _, R ¹⁰ , R ¹¹ and R ¹² are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.

In an embodiment of the invention herein, in formula (II), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^5′ , R ^6′ , R ^7′ , R ^8′ _, R ¹⁰ , R ¹¹ and R ¹² is each independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl, dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthalen-2-yl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.

In an embodiment of the invention herein, in formula (II), M is Hf or Zr, E and E' are O; R ¹ and R ^1' are each independently C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom or a heteroatom containing group;
R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^2' , R ^3' , and R ^4' are each independently hydrogen, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ substituted hydrocarbyl, a heteroatom or a heteroatom containing group, or one or more of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^1' and R ^2' , R ^2' and R ^3' , R ^3' and R ^4' may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, or substituted heterocyclic rings, unsubstituted heterocyclic rings having 5, 6, 7, or 8 ring atoms, respectively, and substituents on the rings may be joined to form additional rings; R ⁹ is hydrogen, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C 20 substituted hydrocarbyl, a heteroatom or a heteroatom containing group; _20- substituted hydrocarbyl, or heteroatom-containing groups, such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or isomers thereof;
X are each independently a hydrocarbyl group having 1 to 20 carbon atoms (e.g., alkyl or aryl), hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, ether, and combinations thereof (two or more X may form part of a fused ring or ring system); n is 2; m is 0; R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^5′ , R 6 ^′ , R ^7′ , R ^8′ _, R ¹⁰ , R ¹¹ and R ¹² are each independently hydrogen, a C ₁ to C ₂₀ hydrocarbyl, a C ₁ to C 20 alkoxy group ... ₂₀ substituted hydrocarbyl, heteroatom or heteroatom-containing group, or one or more adjacent R groups may combine to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocyclic, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, and substitutions on the rings may combine to form additional rings, e.g., R ⁵ , R ⁶ , R ⁷ , R 8 , R ⁵ ', R ^{6 '} , R ^{7 ' ,} R ⁸ ', R ¹⁰ , R ¹¹ and R Each of ¹² is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, and docosyl; tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl, dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.

A preferred embodiment of formula (I) is where M is Zr or Hf, Q is nitrogen, A ¹ and A ^1' are both carbon, E and E ^' are both oxygen, and R ¹ and R ^1' are both C ₄ -C ₂₀ cyclic tertiary alkyl.

Preferred embodiments of formula (I) are those in which M is Zr or Hf, Q is nitrogen, ^A1 and A1 ^' are both carbon, E and E ^' are both oxygen, and ^R1 and R1 ^' are both adamantan-1-yl or substituted adamantan-1-yl.

Preferred embodiments of formula (I) are those in which M is Zr or Hf, Q is nitrogen, A ¹ and A ^1′ are both carbon, E and E′ are both oxygen, X is methyl or chloro, and n is 2.

A preferred embodiment of formula (II) is where M is Zr or Hf, E and E ^' are both oxygen, and ^R1 and R1 ^' are both _C4 - _C20 cyclic tertiary alkyl.

A preferred embodiment of formula (II) is where M is Zr or Hf, E and E ^' are both oxygen, and ^R1 and R1 ^' are both adamantan-1-yl or substituted adamantan-1-yl.

A preferred embodiment of formula (II) is where M is Zr or Hf, E and E ^' are both oxygen, and each of R ¹ , R ¹ , R ³ and R ^3' is adamantan-1-yl or substituted adamantan-1-yl.

A preferred embodiment of formula (II) is where M is Zr or Hf, E and E ^' are both oxygen, ^R1 and R1 ^' are both _C4 - _C20 cyclic tertiary alkyl, and ^R7 and R7 ^' are both _C1 - _C20 alkyl.

Particularly useful catalyst compounds in the present invention are dimethylzirconium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-oleate], dimethylhafnium [2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-oleate], ester)], dimethylzirconium [6,6'-(pyridine-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-adamantan-1-yl)-4-methylphenolate)], dimethylhafnium [6,6'-(pyridine-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-adamantan-1-yl)-4-methylphenolate)], dimethylzirconium [ 2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl))-5-methyl-[1,1'-biphenyl]-2-olate)], dimethylhafnium[2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-olate)], dimethylzirconium[2', Contains one or more of 2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-4',5-dimethyl-[1,1'-biphenyl]-2-olate)] and dimethylhafnium[2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-4',5-dimethyl-[1,1'-biphenyl]-2-olate)].

Particularly useful catalyst compounds in the present invention include compounds represented by one or more of the following formulas:

In some embodiments, two or more different catalyst compounds are present in the catalyst systems used herein. In some embodiments, two or more different catalyst compounds are present in the reaction zone in which the processes described herein occur. Although it is preferred to use the same activator for the transition metal compound, two different activators can be used in combination, for example, a non-coordinating anion activator and an alumoxane. When one or more transition metal compounds contain an X group that is not a hydride, hydrocarbyl, or substituted hydrocarbyl, the alumoxane can be contacted with the transition metal compound prior to the addition of the non-coordinating anion activator.

The two transition metal compounds (pre-catalysts) can be used in any ratio. Preferred molar ratios of (A) transition metal compound to (B) transition metal compound (A:B) fall within the range of 1:1000-1000:1, or 1:100-500:1, or 1:10-200:1, or 1:1-100:1, or 1:1-75:1, or 5:1-50:1. The particular ratio selected will depend on the exact pre-catalyst selected, the method of activation, and the desired end product. In certain embodiments, when using two pre-catalysts, both of which are activated with the same activator, useful mole percentages based on the molecular weight of the pre-catalyst are 10-99.9% A: 0.1-90% B, or 25-99% A: 0.5-50% B, or 50-99% A: 1-25% B, or 75-99% A: 1-10% B.

［式中、Ｍ’は１、２、１２、または１３族の元素、またはＬｉ、ＭｇＣｌ、ＭｇＢｒ、ＺｎＣｌ、Ｂ（ＯＨ）^２、Ｂ（ピナコラート）などの置換元素であり、Ｐはメトキシメチル（ＭＯＭ）、テトラヒドロピラニル（ＴＨＰ）、ｔ－ブチル、アリル、エトキシメチル、トリアルキルシリル、ｔ－ブチルジメチルシリル、またはベンジルなどの保護基であり、Ｒは、Ｃ_１～Ｃ_４０アルキル、置換アルキル、アリール、第三級アルキル、環状第三級アルキル、アダマンタニル、または置換アダマンタニルであり、Ｘ’およびＸは、それぞれ、Ｃｌ、Ｂｒ、Ｆ、またはＩなどのハロゲンである。］ Method for producing catalyst compound
Ligand Synthesis Bis(phenol) ligands can be prepared using the general methodology shown in Scheme 1. Coupling of Compound A with Compound B to form the bis(phenol) ligand (Method 1) can be achieved by known Pd- and Ni-catalyzed couplings, such as Negishi, Suzuki, Kumada, etc. Coupling of Compound C with Compound D to form the bis(phenol) ligand (Method 2) can be achieved by known Pd- and Ni-catalyzed couplings, such as Negishi, Suzuki, Kumada, etc. Compound D can be prepared from Compound E by reaction of Compound E with an organolithium reagent or magnesium metal, followed by optional reaction with a main group metal halide (e.g. ZnCl ₂ ) or boron-based reagent (e.g. B(O ⁱ Pr) ₃ , ⁱ PrOB(pin)). Compound E can be prepared in a non-catalyzed reaction by the reaction of an aryl lithium or aryl Grignard reagent (compound F) with a dihalogenated arene such as 1-bromo-2-chlorobenzene (compound G). Compound E can also be prepared in a Pd or Ni catalyzed reaction by the reaction of an aryl zinc or aryl boron reagent (compound F) with a dihalogenated arene (compound G).

Scheme 1

where M' is a Group 1, 2, 12, or 13 element or a substituted element such as Li, MgCl, MgBr, ZnCl, B(OH) ² , B(pinacolato), P is a protecting group such as methoxymethyl (MOM), tetrahydropyranyl (THP), t-butyl, allyl, ethoxymethyl, trialkylsilyl, t-butyldimethylsilyl, or benzyl, R is C ₁ -C ₄₀ alkyl, substituted alkyl, aryl, tertiary alkyl, cyclic tertiary alkyl, adamantanyl, or substituted adamantanyl, and X' and X are each a halogen such as Cl, Br, F, or I.

Bis(phenol) ligands and intermediates used in the preparation of bis(phenol) ligands are preferably prepared and purified without the use of column chromatography. This can be accomplished by a variety of methods including distillation, precipitation and washing, formation of insoluble salts (e.g., by reaction of pyridine derivatives with organic acids), and liquid-liquid extraction. Preferred methods include those described in Practical Process Research and Development - A Guide for Organic Chemists by Neal C. Anderson (ISBN: 1493300125X).

Synthesis of Carbene Bis(phenol) Ligands A general synthetic method for the synthesis of carbene bis(phenol) ligands is shown in Scheme 2. Substituted phenols are ortho-brominated and then protected with known phenol protecting groups such as methoxymethyl ether (MOM), tetrahydropyranyl ether (THP), t-butyldimethylsilyl (TBDMS), benzyl (Bn), etc. The bromide is then converted to a boronic ester (compound I) or boronic acid that can be used in Suzuki coupling with bromoanilines. Biphenylanilines (compound J) are crosslinked and deprotected (compound K) by reaction with dibromoethane or condensation with oxalaldehyde. Reaction with triethyl orthoformate forms an iminium salt, which is then deprotected to the carbene.

Scheme 2

To the substituted phenol (compound H) dissolved in methylene chloride is added an equivalent of N-bromosuccinimide and 0.1 equivalent of diisopropylamine. After stirring at ambient temperature until complete, the reaction is quenched with 10% HCl solution. The organic portion is washed with brine, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to give the bromophenol, typically as a solid. The substituted bromophenol, methoxymethyl chloride, and potassium carbonate are dissolved in dry acetone and stirred at ambient temperature until the reaction is complete. The solution is filtered, and the filtrate is concentrated to give the protected phenol (compound I). Alternatively, the substituted bromophenol and an equivalent of dihydropyran are dissolved in methylene chloride and cooled to 0°C. A catalytic amount of paratoluenesulfonic acid is added and the reaction is stirred for 10 minutes and then quenched with trimethylamine. The mixture is washed with water and brine, then dried over magnesium sulfate, filtered, and concentrated under reduced pressure to give the tetrahydropyran protected phenol.

The aryl bromide (compound I) is dissolved in THF and cooled to -78°C. n-Butyllithium is slowly added followed by trimethoxyborate. The reaction is stirred at ambient temperature until completion. The solvent is removed and the solid boronic ester is washed with pentane. Boronic acids can be prepared from boronic esters by treatment with HCl. The boronic ester or acid is dissolved in toluene with an equivalent amount of orthobromoaniline and a catalytic amount of palladium tetrakistriphenylphosphine. An aqueous solution of sodium carbonate is added and the reaction is heated to reflux overnight. After cooling, the layers are separated and the aqueous layer is extracted with ethyl acetate. The combined organic portions are washed with brine, dried (MgSO ₄ ), filtered and concentrated under reduced pressure. Column chromatography is typically used to purify the coupled product (compound J).

Aniline (compound J) and dibromoethane (0.5 equiv.) are dissolved in acetonitrile and heated at 60°C overnight. The reaction is filtered and concentrated to give the ethylene-bridged dianiline. The protected phenol is deprotected by reaction with HCl to give the bridged bisamino(biphenyl)ol (compound K).

The diamine (compound K) is dissolved in triethyl orthoformate. Ammonium chloride is added and the reaction is heated to reflux overnight. A precipitate forms which is collected by filtration and washed with ether to give the iminium salt. The iminium chloride is suspended in THF and treated with lithium or sodium hexamethyldisilylamide. Upon completion, the reaction is filtered and the filtrate is concentrated to give the carbene ligand.

Preparation of Bis(phenolate) Complexes Transition metal or lanthanide metal bis(phenolate) complexes are used as catalyst components for olefin polymerization in the present invention. The terms "catalyst" and "catalyst complex" are used interchangeably. Preparation of transition metal or lanthanide metal bis(phenolate) complexes can be accomplished by reaction of a bis(phenol) ligand with a metal reactant that contains an anionic basic leaving group. Typical anionic basic leaving groups include dialkylamide, benzyl, phenyl, hydride, and methyl. In this reaction, the role of the basic leaving group is to deprotonate the bis(phenol) ligand. Metal reactants suitable for this type of reaction include, but are not limited _to , _HfBn4 (Bn= _CH2Ph ), _ZrBn4 , _TiBn4 , _{ZrBn2Cl2 (} OEt2), HfBn2Cl2( _OEt2 ) ₂ , Zr( _NMe2 ) _2Cl2 (dimethoxyethane), Zr( _NEt2 ) _2Cl2 ( _{dimethoxyethane} ), _{Hf ( NEt2} ) _2Cl2 (dimethoxyethane), Hf( _{NMe2 ) 2Cl2} ( _{dimethoxyethane} ), Hf( _NMe2 ) ₄ , Zr( _NMe2 ) ₄ , and Hf _{(NEt2 ) 4} . Suitable metal reagents also include _ZrMe4 , _HfMe4 , and other Group 4 alkyls which may be formed in situ and used without isolation. Preparation of the transition metal bis(phenolate) complexes is typically carried out in an ether or hydrocarbon solvent or solvent mixture, typically at temperatures in the range of -80°C to 120°C.

A second method for preparing transition metal or lanthanide bis(phenolate) complexes is by reacting the bis(phenol) ligand with an alkali metal or alkaline earth metal base (e.g., Na, BuLi, ^iPrMgBr ) to give the deprotonated ligand, followed by reaction with a metal halide (e.g., HfCl ₄ , ZrCl ₄ ) to form the bis(phenolate) complex. Bis(phenolate) metal complexes containing metal halide, alkoxide, or amide leaving groups can be alkylated by reaction with organolithium, Grignard, and organoaluminum reagents. In the alkylation reaction, the alkyl group is transferred to the bis(phenolate) metal center and the leaving group is removed. Reagents typically used for alkylation reactions include, but are not limited to, MeLi, MeMgBr, AlMe ₃ , Al( ⁱ Bu) ₃ , AlOct ₃ , and PhCH ₂ MgCl. Typically, 2 to 20 molar equivalents of the alkylating agent are added to the bis(phenolate) complex. The alkylation is generally carried out in an ether or hydrocarbon solvent or solvent mixture, typically at temperatures in the range of -80°C to 120°C.

Activators The terms "cocatalyst" and "activator" are used interchangeably herein.

The catalyst systems described herein typically include a catalyst complex, such as the transition metal or lanthanide bis(phenolate) complexes described above, and an activator, such as an alumoxane or a non-coordinating anion. These catalyst systems can be formed by combining the catalyst components described herein with an activator in any manner known in the literature. The catalyst systems can also be added to or formed in solution or bulk polymerizations (in monomer). The catalyst systems of the present disclosure can have one or more activators and one, two or more catalyst components. An activator is defined as any compound capable of activating any one of the above catalyst compounds by converting a neutral metal compound to a catalytically active metal compound cation. Non-limiting activators include, for example, alumoxanes, ionizing activators, which can be neutral or ionic, and conventional cocatalysts. Preferred activators typically include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract reactive metal ligands, cationize the metal compound, and provide a non-coordinating or weakly coordinating anion, such as a non-coordinating anion, that balances the charge.

Alumoxane Activators Alumoxane activators are utilized as activators in the catalyst systems described herein. Alumoxanes are generally oligomeric compounds containing -Al(R ⁹⁹ )-O- subunits, where R ⁹⁹ is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, especially when the abstractable ligand is an alkyl, halide, alkoxide, or amide. Mixtures of different alumoxanes and modified alumoxanes can also be used. It is preferred to use visually clear methylalumoxane. Cloudy or gelled alumoxanes can be filtered to produce a clear solution, or clear alumoxane can be decanted from the cloudy solution. A useful alumoxane is modified methylalumoxane (MMAO) catalyst type 3A (covered in U.S. Pat. No. 5,041,584 and commercially available from Akzo Chemicals, Inc. under the trade name "Modified Methylalumoxane type 3A"). Another useful alumoxane is solid polymethylaluminoxane, which is described in U.S. Pat. Nos. 9,340,630, 8,404,880; and 8,975,209.

When the activator is an alumoxane (modified or unmodified), typically the maximum amount of activator is up to a 5000-fold molar excess of Al/M relative to the catalyst compound (per metal catalyst site). The minimum molar ratio of activator to catalyst compound is 1:1. Alternative preferred ranges include 1:1 to 500:1, or 1:1 to 200:1, or 1:1 to 100:1, or 1:1 to 50:1.

In another embodiment, little or no alumoxane is used in the polymerization processes described herein. Preferably, the alumoxane is present at zero mole percent, or the alumoxane is present at a molar ratio of aluminum to transition metal of the catalyst compound of less than 500:1, preferably less than 300:1, preferably less than 100:1, preferably less than 1:1.

Ionizing/Non-Coordinating Anion Activators The term "non-coordinating anion" (NCA) refers to an anion that does not coordinate to a cation or that only weakly coordinates to a cation, thereby remaining sufficiently labile to be displaced by a neutral Lewis base. Furthermore, the anion does not transfer an anionic substituent or fragment to the cation to form a neutral transition metal compound and a neutral by-product from the anion. Useful non-coordinating anions of the present invention are those that are compatible and stabilize the transition metal cation in the sense of balancing the ionic charge with +1, yet retain sufficient lability to allow for displacement during polymerization. The term NCA is also defined to include multi-component NCA-containing activators, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, which contain an acidic cationic group and a non-coordinating anion. The term NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, which can react with the catalyst to form an activated species by abstraction of an anionic group. Any metal or metalloid capable of forming a compatible weakly coordinating complex may be used or contained in the non-coordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon.

It is within the scope of the present invention to use neutral or ionic ionizing activators. It is also within the scope of the present invention to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.

［式中、Ｚは（Ｌ－Ｈ）または還元可能なルイス酸であり、Ｌは中性のルイス塩基であり；Ｈは水素であり；（Ｌ－Ｈ）^＋はブレンステッド酸であり；Ａ^ｄ－は、電荷ｄ－を持つ非配位アニオンであり；ｄは１～３までの整数（例えば、１、２または３）であり、好ましくは、Ｚは（Ａｒ_３Ｃ^＋）であり、ここでＡｒはアリールまたはヘテロ原子で置換されたアリール、Ｃ_１～Ｃ_４０ヒドロカルビル、または置換Ｃ_１～Ｃ_４０ヒドロカルビルである］。アニオン成分Ａ^ｄ－には、式［Ｍ^ｋ＋Ｑ_ｎ］^ｄ－を有するものが含まれる。式中、ｎは１、２、３、４、５、または６（好ましくは１、２、３、または４）であり；ｎ－ｋ＝ｄ；Ｍは、元素の周期表の第１３族から選択される元素、好ましくはホウ素またはアルミニウムであり、Ｑは、独立して、水素化物、架橋または非架橋ジアルキルアミド、ハロゲン化物、アルコキシド、アリールオキシド、ヒドロカルビル、置換ヒドロカルビル、ハロカルビル、置換ハロカルビル、およびハロ置換ヒドロカルビル基であり、Ｑは４０個までの炭素原子を有する（任意に、ただし、１回以下の出現でＱがハロゲン化物である）。好ましくは、各Ｑは、１～４０個（例えば１～２０個）の炭素原子を有するフッ素化ヒドロカルビル基であり、より好ましくは、各Ｑはパーフルオロアリール基などのフッ素化アリール基であり、最も好ましくは、各Ｑはペンタフルオロアリール基またはパーフルオロナフタレン－２－イル基である。適切なＡ^ｄ－の例には、米国特許第５，４４７，８９５号に開示されているジボロン化合物が含まれ、これは参照により本明細書に完全に組み込まれる。 In an embodiment of the present invention, the activator is represented by formula (III):

where Z is (LH) or a reducible Lewis acid, L is a neutral Lewis base; H is hydrogen; (LH) ⁺ is a Bronsted acid; A ^d - is a non-coordinating anion carrying a charge d-; d is an integer from 1 to 3 (e.g., 1, 2 or 3), and preferably Z is (Ar ₃ C ⁺ ), where Ar is aryl or heteroatom substituted aryl, C ₁ -C ₄₀ hydrocarbyl, or substituted C ₁ -C ₄₀ hydrocarbyl. Anionic components A ^d - include those having the formula [M ^k+ Q _n ] ^d -. wherein n is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4); n-k=d; M is an element selected from Group 13 of the Periodic Table of the Elements, preferably boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halo-substituted hydrocarbyl group having up to 40 carbon atoms (optionally, but with the exception that in no more than one occurrence Q is a halide). Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 40 (e.g. 1 to 20) carbon atoms, more preferably each Q is a fluorinated aryl group such as a perfluoroaryl group, and most preferably each Q is a pentafluoroaryl group or a perfluoronaphthalene-2-yl group. Examples of suitable A ^d - include the diboron compounds disclosed in US Pat. No. 5,447,895, which is hereby incorporated by reference in its entirety.

When Z is an activating cation (L-H), it may be a Bronsted acid capable of donating a proton to a transition metal catalyst precursor to produce a transition metal cation, and may be an ammonium compound, an oxonium compound, a phosphonium compound, a sulfonium compound, and mixtures thereof, such as methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, N-methyl-4-nonadecyl-N-octadecylaniline, N-methyl-4-octadecyl-N-octadecylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethyl ... These include ammonium compounds derived from ammonium dianiline, methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, and dioctadecylmethylamine; phosphonium compounds derived from triethylphosphine, triphenylphosphine, and diphenylphosphine; oxonium compounds derived from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane; and sulfonium compounds derived from thioethers such as sulfonium diethylthioether, tetrahydrothiophene, and mixtures thereof.

In particularly useful embodiments of the invention, the activator is soluble in a non-aromatic hydrocarbon solvent, such as an aliphatic solvent.

In one or more embodiments, a 20% by weight mixture of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear homogeneous solution at 25°C, and preferably a 30% by weight mixture of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear homogeneous solution at 25°C.

In an embodiment of the invention, the activators described herein have a solubility in methylcyclohexane at 25° C. (stirring for 2 hours) of greater than 10 mM (or greater than 20 mM, or greater than 50 mM).

In an embodiment of the invention, the activators described herein have a solubility in isohexane at 25° C. (stirring for 2 hours) of greater than 1 mM (or greater than 10 mM, or greater than 20 mM).

In an embodiment of the invention, the activators described herein have a solubility of greater than 10 mM (or greater than 20 mM, or greater than 50 mM) in methylcyclohexane at 25° C. (2 hours stirring) and greater than 1 mM (or 10 mM or more, or 20 mM or more) in isohexane at 25° C. (2 hours stirring).

In a preferred embodiment, the activator is a non-aromatic hydrocarbon soluble activator compound.

［式中：
Ｅは、窒素またはリンであり；
ｄは、１、２、または３であり；ｋは、１、２、または３であり；ｎは、１、２、３、４、５、または６であり；ｎ－ｋ＝ｄであり（好ましくは、ｄは、１、２、または３であり；ｋは３であり；ｎは、４、５、または６である。）；
Ｒ^１’、Ｒ^２’、およびＲ^３’は、独立して、１つまたは複数の、アルコキシ基、シリル基、ハロゲン原子、またはハロゲン含有基により置換されていてもよい、Ｃ_１～Ｃ_５０ヒドロカルビル基であり；
ここに、Ｒ^１’、Ｒ^２’、およびＲ^３’は、合わせて１５個以上の炭素原子を含み；
Ｍｔは、元素の周期表の第１３族から選択された元素（例えば、ＢまたはＡｌ）であり；
Ｑは、それぞれ独立して、水素化物、架橋または非架橋ジアルキルアミド、ハロゲン化物、アルコキシド、アリールオキシド、ヒドロカルビル、置換ヒドロカルビル、ハロカルビル、置換ハロカルビル、またはハロ置換ヒドロカルビル基である。］ Non-aromatic hydrocarbon soluble activator compounds useful herein include compounds represented by formula (V):

[Wherein:
E is nitrogen or phosphorus;
d is 1, 2, or 3; k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6; and n-k=d (preferably, d is 1, 2, or 3; k is 3; and n is 4, 5, or 6);
R ^1' , R ^2' , and R ^3' are independently C ₁ -C ₅₀ hydrocarbyl groups optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups;
wherein R ^1' , R ^2' , and R ^3' collectively contain 15 or more carbon atoms;
Mt is an element selected from Group 13 of the Periodic Table of the Elements (e.g., B or Al);
Each Q is independently a hydride, a bridged or unbridged dialkylamide, a halide, an alkoxide, an aryloxide, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, or a halo-substituted hydrocarbyl group.

［式中、Ｅは窒素またはリンであり；Ｒ^１’はメチル基であり；Ｒ^２’およびＲ^３’は、独立して、１つまたは複数のアルコキシ基、シリル基、ハロゲン原子、またはハロゲン含有基により置換されていてもよいＣ_４～Ｃ_５０ヒドロカルビル基であり、ここで、Ｒ^２’およびＲ^３’は、一緒になって、１４個以上の炭素原子を含み；Ｂはホウ素であり；Ｒ^４’、Ｒ^５’、Ｒ^６’およびＲ^７’は、独立して、水素化物、架橋または非架橋ジアルキルアミド、ハロゲン化物、アルコキシド、アリールオキシド、ヒドロカルビル、置換ヒドロカルビル、ハロカルビル、置換ハロカルビル、またはハロ置換ヒドロカルビルラジカルである。］ Non-aromatic hydrocarbon soluble activator compounds useful herein include compounds represented by formula (VI):

wherein E is nitrogen or phosphorus; R ^1' is a methyl group; R ^2' and R ^3' are independently a C ₄ -C ₅₀ hydrocarbyl group optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups, where R ^2' and R ^3' together contain 14 or more carbon atoms; B is boron; and R ^4' , R ^5' , R ^6' , and R ^7' are independently a hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halo-substituted hydrocarbyl radical.

および

［式中：
Ｎは窒素であり、
Ｒ^２’およびＲ^３’は、独立して、１つまたは複数のアルコキシ基、シリル基、ハロゲン原子、またはハロゲン含有基で置換されていてもよいＣ_６～Ｃ_４０ヒドロカルビル基であり、Ｒ^２’およびＲ^３’（存在する場合）は、一緒になって１４個以上の炭素原子を含み；
Ｒ^８’、Ｒ^９’およびはＲ^１０’は、独立して、Ｃ_４～Ｃ_３０ヒドロカルビル基または置換Ｃ_４～Ｃ_３０ヒドロカルビル基であり；
Ｂはホウ素であり；
Ｒ^４’、Ｒ^５’、Ｒ^６’およびＲ^７’は、独立して、水素化物、架橋または非架橋ジアルキルアミド、ハロゲン化物、アルコキシド、アリールオキシド、ヒドロカルビル、置換ヒドロカルビル、ハロカルビル、置換ハロカルビル、またはハロ置換ヒドロカルビル基である。］ Non-aromatic hydrocarbon soluble activator compounds useful herein include those represented by formula (VII) or formula (VIII):

and

[Wherein:
N is nitrogen;
R ^2' and R ^3' are independently a C ₆ -C ₄₀ hydrocarbyl group optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups, and R ^2' and R ^3' (if present) together contain 14 or more carbon atoms;
R ^{8 '} , R ^{9 '} and R ^{10 '} are independently a C ₄ -C ₃₀ hydrocarbyl group or a substituted C ₄ -C ₃₀ hydrocarbyl group;
B is boron;
R ^{4 '} , R ^{5 '} , R ^{6 '} and R ^{7 '} are independently a hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halo-substituted hydrocarbyl group.

Optionally, in any of formulas (V), (VI), (VII), or (VIII) herein, R ^{4 '} , R ^{5 '} , R ^{6 '} and R ^{7 '} are pentafluorophenyl.

Optionally, in any of formulas (V), (VI), (VII), or (VIII) R ^{4 '} herein, R ^{4 '} , R ^{5 '} , R ^{6 '} and R ^{7 '} are pentafluoronaphthalen-2-yl.

Optionally, in the embodiment of formula (VIII) herein, R ^8' and R ^10' are hydrogen atoms and R ^9' is a C ₄ -C ₃₀ hydrocarbyl group optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups.

Optionally, in an embodiment of Formula (VIII) herein, R ^{9 '} is a C ₈ -C ₂₂ hydrocarbyl group optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups.

Optionally, in the embodiments of formula (VII) or (VIII) herein, R ^2' and R ^3' are independently C ₁₂ -C ₂₂ hydrocarbyl groups.

Optionally, R ^1' , R ^2' and R ^3' together contain 15 or more carbon atoms (e.g., 18 or more carbon atoms, 20 or more carbon atoms, 22 or more carbon atoms, 25 or more carbon atoms, 30 or more carbon atoms, 35 or more carbon atoms, 38 or more carbon atoms, 40 or more carbon atoms, 15 to 100 carbon atoms, 25 to 75 carbon atoms).

Optionally, R ^2' and R ^3' together contain 15 or more carbon atoms (e.g., 18 or more carbon atoms, 20 or more carbon atoms, 22 or more carbon atoms, 25 or more carbon atoms, 30 or more carbon atoms, 35 or more carbon atoms, 38 or more carbon atoms, 40 or more carbon atoms, 15 to 100 carbon atoms, 25 to 75 carbon atoms).

Optionally, R ^8' , R ^9' and R ^10' together contain 15 or more carbon atoms (e.g., 18 or more carbon atoms, 20 or more carbon atoms, 22 or more carbon atoms, 25 or more carbon atoms, 30 or more carbon atoms, 35 or more carbon atoms, 38 or more carbon atoms, 40 or more carbon atoms, 15 to 100 carbon atoms, 25 to 75 carbon atoms).

Optionally, when Q is a fluorophenyl group, R ^2' is not a C ₁ -C ₄₀ straight chain alkyl group (or R ^2' is not an optionally substituted C ₁ -C ₄₀ straight chain alkyl group).

Optionally, R ^4' , R ^5' , R ^6' and R ^7' are each an aryl group (e.g., phenyl or naphthalene-2-yl) and at least one of R ^4' , R ^5' , R ^6' and R ⁷ ' is substituted with at least one fluorine atom, preferably R ^4' , R ^5' , R ^6' and R ^7' are each a perfluoroaryl group (e.g., perfluorophenyl or perfluoronaphthalene-2-yl).

Optionally, each Q is an aryl group (e.g., phenyl or naphthalene-2-yl) and at least one Q is substituted with at least one fluorine atom, preferably each Q is a perfluoroaryl group (e.g., perfluorophenyl or perfluoronaphthalene-2-yl).

Optionally, R ^1' is a methyl group; R ^2' is a C ₆ -C ₅₀ aryl group; and R ^3' is independently a C ₁ -C ₄₀ linear alkyl or a C ₅ -C ₅₀ aryl group.

Optionally, R ^2' and R ^3' are each independently unsubstituted or substituted with at least one of halide, C ₁ -C ₃₅ alkyl, C ₅ -C ₁₅ aryl, C ₆ -C ₃₅ arylalkyl, C 6 -C ₃₅ alkylaryl, and R ₂ ^' and R ^3' contain 20 or more carbon atoms.

Optionally, Q is independently a hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halo-substituted-hydrocarbyl radical, with the proviso that when Q is a fluorophenyl group, R ^2' is not a C ₁ -C ₄₀ straight chain alkyl group, preferably R ^2' is not an optionally substituted C ₁ -C 40 straight chain alkyl group (or when Q is a substituted phenyl group, R ^2' is not a C ₁ -C ₄₀ straight chain alkyl group, preferably R ^2' is not an optionally substituted C ₁ -C 40 straight chain alkyl group). Optionally, when Q is a fluorophenyl group (or when Q is a substituted phenyl group), R ^2′ is a meta- and/or para-substituted phenyl group, the meta and para substituents being independently an optionally substituted C ₁ to C ₄₀ hydrocarbyl group (e.g. a C ₆ to C ₄₀ aryl or straight chain alkyl group, a C ₁₂ to C ₃₀ aryl or straight chain alkyl group, a C ₁₀ to C ₂₀ aryl or straight chain alkyl group), an optionally substituted alkoxy group, or an optionally substituted silyl group. Optionally, Q is a fluorinated hydrocarbyl group having from 1 to 30 carbon atoms, more preferably each Q is a fluorinated aryl group (such as phenyl or naphthalene-2-yl), and most preferably each Q is a perfluoroaryl group (such as phenyl or naphthalene-2-yl). Examples of suitable [Mt ^k+ Q _n ] ^d - also include the diboron compounds disclosed in U.S. Patent No. 5,447,895, which is incorporated herein by reference in its entirety. Optionally, at least one Q is not a substituted phenyl. Optionally, all of Q are not a substituted phenyl. Optionally, at least one Q is not a perfluorophenyl. Optionally, all of Q are not a perfluorophenyl.

In some embodiments of the invention, R ^1' is not methyl, R ^2' is not C ₁₈ alkyl, and R ^3' is not C ₁₈ alkyl; or, R ^1' is not methyl, R ^2' is not C ₁₈ alkyl, R ^3' is not C ₁₈ alkyl, and at least one Q is not substituted phenyl, and optionally all of Q are not substituted phenyl.

Useful cationic moieties in formula (III) and formulas (V)-(VIII) include those represented by the following formula:

本明細書に記載の活性化剤のアニオン成分は、式［Ｍｔ^ｋ＋Ｑ_ｎ］^ｄ－により表されるものを含む。式中、ｋは１、２、または３であり；ｎは１、２、３、４、５、または６であり（好ましくは１、２、３、または４）、（好ましくはｋはであり；ｎは４、５、または６であり、好ましくはＭがＢである場合、ｎは４である）；Ｍｔは、元素の周期表の第１３族から選択される元素であり、好ましくはホウ素またはアルミニウムであり、Ｑは、独立して、水素化物、架橋または非架橋ジアルキルアミド、ハロゲン化物、アルコキシド、アリールオキシド、ヒドロカルビル、置換ヒドロカルビル、ハロカルビル、置換ハロカルビル、およびハロ置換ヒドロカルビルラジカルであり、該Ｑは、２０個までの炭素原子を有し、ただし、１回以下の出現でＱはハロゲン化物である。好ましくは、Ｑは、それぞれ、１～２０個の炭素原子を有していてもよいフッ素化ヒドロカルビル基であり、より好ましくは、Ｑは、それぞれ、フッ素化アリール基であり、最も好ましくは、Ｑは、それぞれパーフルオロアリール基である。好ましくは、少なくとも１つのＱは、パーフルオロフェニルなどの置換フェニルではなく、好ましくはＱのすべては、パーフルオロフェニルなどの置換フェニルではない。 Useful cationic moieties in formula (III) and formulas (V)-(VIII) include those represented by the following formula:

Anionic components of the activators described herein include those represented by the formula [Mt ^k+ Q _n ] ^d -, where k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4), (preferably k is; n is 4, 5, or 6, preferably when M is B, n is 4); Mt is an element selected from Group 13 of the Periodic Table of the Elements, preferably boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halo-substituted hydrocarbyl radical, said Q having up to 20 carbon atoms, with the proviso that in not more than one occurrence Q is a halide. Preferably, each Q is a fluorinated hydrocarbyl group optionally having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a perfluoroaryl group. Preferably, at least one Q is not a substituted phenyl such as perfluorophenyl, and preferably all of Q are not substituted phenyl such as perfluorophenyl.

In one embodiment, the borate activator comprises tetrakis(heptafluoronaphth-2-yl)borate.

In one embodiment, the borate activator comprises tetrakis(pentafluorophenyl)borate.

［式中：
Ｍ^＊は、第１３族原子、好ましくはＢまたはＡｌ、好ましくはＢであり；
Ｒ^１１は、それぞれ独立して、ハロゲン化物、好ましくはフッ化物であり；
Ｒ^１２は、それぞれ独立して、ハロゲン化物、Ｃ_６～Ｃ_２０置換芳香族ヒドロカルビル基、または式－Ｏ－Ｓｉ－Ｒ^ａであらわされるシロキシ基であり、ここに、Ｒ^ａはＣ_１～Ｃ_２０ヒドロカルビルまたはヒドロカルビルシリル基であり、好ましくはＲ^１２はフッ化物またはパーフルオロフェニル基であり；
Ｒ^１３は、それぞれ、ハロゲン化物、Ｃ_６～Ｃ_２０置換芳香族ヒドロカルビル基、または式－Ｏ－Ｓｉ－Ｒ^ａで表されるシロキシ基であり、ここに、Ｒ^ａはＣ_１～Ｃ_２０ヒドロカルビルまたはヒドロカルビルシリル基であり、好ましくはＲ^１３は、フッ化物またはＣ_６パーフルオロ芳香族ヒドロカルビル基であり；
ここで、Ｒ^１２およびＲ^１３は、１つまたは複数の飽和または不飽和の置換または非置換環を形成していてもよく、好ましくはＲ^１２およびＲ^１３はパーフルオロ化フェニル環を形成する。好ましくは、アニオンは、７００ｇ／モルより大きい分子量を有し、好ましくは、Ｍ^＊原子上の少なくとも３つの置換基は、それぞれ、１８０立方Åより大きい分子体積を有する。］ Anions for use in the non-coordinating anion activators described herein include those represented by Formula 7:

[Wherein:
M ^* is a group 13 atom, preferably B or Al, preferably B;
R ¹¹ is independently a halide, preferably a fluoride;
each R ¹² is independently a halide, a C ₆ -C ₂₀ substituted aromatic hydrocarbyl group, or a siloxy group represented by the formula -O-Si-R ^a , where R ^a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbylsilyl group, preferably R ¹² is a fluoride or perfluorophenyl group;
R ¹³ is independently a halide, a C ₆ to C ₂₀ substituted aromatic hydrocarbyl group, or a siloxy group represented by the formula -O-Si-R ^a , where R ^a is a C ₁ to C ₂₀ hydrocarbyl or hydrocarbylsilyl group, preferably R ¹³ is a fluoride or a C ₆ perfluoroaromatic hydrocarbyl group;
wherein R ¹² and R ¹³ may form one or more saturated or unsaturated, substituted or unsubstituted rings, preferably R ¹² and R ¹³ form a perfluorinated phenyl ring. Preferably, the anion has a molecular weight greater than 700 g/mol, and preferably at least three substituents on the M ^* atom each have a molecular volume greater than 180 cubic Å.

"Molecular volume" is used herein as an approximation of the spatial steric volume of an activator molecule in solution. When comparing substituents with different molecular volumes, the substituent with the smaller molecular volume is considered "less bulky" compared to the substituent with the larger molecular volume. Conversely, the substituent with the larger molecular volume can be considered "more bulky" than the substituent with the smaller molecular volume.

Molecular volumes can be calculated as described in "A Simple "Back of the Envelope" Method for Estimating the Densities and Molecular Volumes of Liquids and Solids" Journal of Chemical Education, Vol. 71(11), Nov. 1994, pp. 962-964. Molecular volumes (MV) in cubic Å are calculated using the formula: MV = 8.3 V _s , where V _s is the scaled volume. V _s is the sum of the relative volumes of the constituent atoms and is calculated from the molecular formula of the substituents using Table A of relative volumes below. For fused rings, V _s is reduced by 7.5% for each fused ring. The calculated total MV of the anion is the sum of the MVs per substituent. For example, the MV of perfluorophenyl is 183 Å ³ and the calculated total MV of tetrakis(perfluorophenyl)borate is four times 183 Å ³ , or 732 Å ³ .

Activators can be added to the polymerization in the form of ion pairs, for example, using [M2HTH] ⁺ [NCA]-, where di(hydrogenated tallow)methylamine ("M2HTH") cation reacts with a basic leaving group on the transition metal complex to form the transition metal complex cation and [NCA]-. Alternatively, the transition metal complex can be reacted with a neutral NCA precursor, such as B(C ₆ F ₅ ) ₃ , to abstract an anionic group from the complex to form the activated species. Useful activators include di(hydrogenated tallow)methylammonium [tetrakis(pentafluorophenyl)borate] (i.e., [M2HTH]B(C ₆ F ₅ ) ₄ ) and di(octadecyl)tolylammonium [tetrakis(pentafluorophenyl)borate] (i.e., [DOdTH]B(C ₆ F ₅ ) ₄ ).

Activator compounds particularly useful in the present invention include one or more of the following compounds:
N,N-di(hydrogenated tallow)methylammonium [tetrakis(perfluorophenyl)borate],
N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],
N-methyl-4-hexadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],
N-methyl-4-tetradecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],
N-methyl-4-dodecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],
N-methyl-4-decyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],
N-methyl-4-octyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],
N-methyl-4-hexyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],
N-methyl-4-butyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],
N-methyl-4-octadecyl-N-decylanilinium [tetrakis(perfluorophenyl)borate],
N-methyl-4-nonadecyl-N-dodecylanilinium [tetrakis(perfluorophenyl)borate],
N-methyl-4-nonadecyl-N-tetradecylanilinium [tetrakis(perfluorophenyl)borate],
N-methyl-4-nonadecyl-N-hexadecylanilinium [tetrakis(perfluorophenyl)borate],
N-ethyl-4-nonadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],
N-methyl-N,N-dioctadecylammonium [tetrakis(perfluorophenyl)borate],
N-methyl-N,N-dihexadecylammonium [tetrakis(perfluorophenyl)borate],
N-methyl-N,N-ditetradecylammonium [tetrakis(perfluorophenyl)borate],
N-methyl-N,N-didodecylammonium [tetrakis(perfluorophenyl)borate],
N-methyl-N,N-didecylammonium [tetrakis(perfluorophenyl)borate],
N-methyl-N,N-dioctylammonium [tetrakis(perfluorophenyl)borate],
N-ethyl-N,N-dioctadecylammonium [tetrakis(perfluorophenyl)borate],
N,N-di(octadecyl)tolylammonium [tetrakis(perfluorophenyl)borate],
N,N-di(hexadecyl)tolylammonium [tetrakis(perfluorophenyl)borate],
N,N-di(tetradecyl)tolylammonium [tetrakis(perfluorophenyl)borate],
N,N-di(dodecyl)tolylammonium [tetrakis(perfluorophenyl)borate],
N-octadecyl-N-hexadecyl-tolylammonium [tetrakis(perfluorophenyl)borate],
N-octadecyl-N-hexadecyl-tolylammonium [tetrakis(perfluorophenyl)borate],
N-octadecyl-N-tetradecyl-tolylammonium [tetrakis(perfluorophenyl)borate],
N-octadecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate],
N-octadecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate],
N-hexadecyl-N-tetradecyl-tolylammonium [tetrakis(perfluorophenyl)borate],
N-hexadecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate],
N-hexadecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate],
N-tetradecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate],
N-tetradecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate],
N-dodecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate],
N-methyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate],
N-methyl-N-hexadecylanilinium [tetrakis(perfluorophenyl)borate],
N-methyl-N-tetradecylanilinium [tetrakis(perfluorophenyl)borate],
N-methyl-N-dodecylanilinium [tetrakis(perfluorophenyl)borate],
N-methyl-N-decylanilinium [tetrakis(perfluorophenyl)borate], and N-methyl-N-octylanilinium [tetrakis(perfluorophenyl)borate]

Additional useful activators and synthetic non-aromatic hydrocarbon soluble activators are described in USSN 16/394,166, filed April 25, 2019, USSN 16/394,186, filed April 25, 2019, and USSN 16/394,197, filed April 25, 2019, which are incorporated herein by reference.

Similarly, particularly useful activators include dimethylanilinium tetrakis(pentafluorophenyl)borate and dimethylanilinium tetrakis(heptafluoronaphthalen-2-yl)borate. For a more detailed description of useful activators, see WO 2004/026921, pages 72, paragraph [00119] to 81, paragraph [00151]. A list of further useful activators that can be used in the practice of the present invention can be found in WO 2004/046214, pages 72, paragraph [00177] to 74, paragraph [00178].

For a description of useful activators, see US 8,658,556 and US 6,211,105.

Preferred activators for use herein are N-methyl-4-nonadecyl-N-octadecylbenzeneaminium tetrakis(pentafluorophenyl)borate, N-methyl-4-nonadecyl-N-octadecylbenzeneaminium tetrakis(perfluoronaphthalen-2-yl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthalen-2-yl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthalen-2-yl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Me ₃ NH ⁺ ][B(C ₆ F ₅ ) ₄ −]; 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium; tetrakis(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In a preferred embodiment, the activator comprises a triarylcarbenium (e.g., triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthalen-2-yl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In other embodiments, the activator is one or more of trialkylammonium pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(perfluoronaphthalene-2-yl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dialkylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthalene-2-yl)borate, N, N-dialkylanilinium tetrakis(perfluoronaphthalene-2-yl)borate, trialkylammonium tetrakis(perfluorobiphenyl)borate, N,N-dialkylanilinium tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate (wherein alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, or t-butyl).

Typical activator to catalyst ratios, e.g., all NCA activator to catalyst ratios, are about 1:1 molar ratio. Alternative preferred ranges include 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to 500:1, or 1:1 to 1000:1. Particularly useful ranges are 0.5:1 to 10:1, preferably 1:1 to 5:1.

It is also within the scope of this disclosure that the catalyst compound can be combined with a combination of an alumoxane and an NCA (see, for example, US 5,153,157; US 5,453,410; EP 0573120 B1; WO 1994/007928; and WO 1995/014044, which describe the use of an alumoxane in combination with an ionizing activator), the disclosures of which are incorporated herein by reference in their entireties.

In addition to the optional scavenger, coactivator, and chain transfer agent activator compounds, scavengers or coactivators can be used. Scavenger is typically a compound added to remove impurities and promote polymerization. Some scavengers can also function as activators and are also called coactivators. Coactivators that are not scavengers can also be used in combination with activators to form active catalysts. In some embodiments, the coactivator can be premixed with the transition metal compound to form an alkylated transition metal compound.

Coactivators include alumoxanes such as methylalumoxane, modified alumoxanes such as modified methylalumoxane, and alkylaluminums such as trimethylaluminum, triisobutylaluminum, triethylaluminum, and triisopropylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, or tri-n-dodecylaluminum. Coactivators are typically used in combination with Lewis acid activators and ionic activators when the precatalyst is not a dihydrocarbyl or dihydride complex. Coactivators are also often used as scavengers to inactivate impurities in the feed or reactor.

Aluminum alkyl or organoaluminum compounds that can be used as scavengers or coactivators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and dialkylzincs such as diethylzinc.

Chain transfer agents can be used in the compositions and/or processes described herein. Useful chain transfer agents are typically hydrogen, alkylalumoxanes of the formula AlR ₃ , ZnR ₂ , where each R is independently a C1-C8 aliphatic radical, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or an isomer thereof, or combinations thereof, such as diethylzinc, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof.

Polymerization Process Solution polymerization processes can be used to carry out the polymerization reactions disclosed herein in any suitable manner known to those skilled in the art. In certain embodiments, the polymerization process can be carried out in a continuous polymerization process. The term "batch" refers to a process in which the complete reaction mixture is removed from the polymerization reaction vessel at the end of the polymerization reaction. In contrast, in a continuous polymerization process, one or more reactants are continuously introduced into the reaction vessel and a solution containing the polymer product is simultaneously or nearly simultaneously removed. Solution polymerization refers to a polymerization process in which the polymer produced is soluble in a liquid polymerization medium, such as an inert solvent or monomer or a blend thereof. Solution polymerizations are typically homogeneous. Homogeneous polymerizations are those in which the polymer product is dissolved in the polymerization medium. Such systems are described in J. Vladimir Oliveira, et al., Ind. Eng. Chem. Res., v.29, 2000, pg. 4627.

In a typical solution process, catalyst components, solvent, monomer, and hydrogen (if used) are fed under pressure to one or more reactors. Temperature control in the reactor is generally obtained by a balance between the heat of polymerization and reactor cooling by reactor jacket or cooling coils to cool the reactor contents, autocooling, pre-cooled feed, reactors cooled by liquid media (diluent, monomer or solvent) or a combination of all three. Adiabatic reactors with pre-cooled feeds can also be used. Monomer is dissolved/dispersed in a solvent before being fed to the first reactor or dissolved in the reaction mixture. Solvent and monomer are generally purified to remove potential catalyst poisons before entering the reactor. The feedstock can be heated or cooled before being fed to the first reactor. Additional monomer and solvent can be added to the second reactor, which can be heated or cooled. Catalyst/activator can be fed to the first reactor or split between the two reactors. In solution polymerization, the polymer produced melts and remains dissolved in the solvent under reactor conditions, forming a polymer solution (also called effluent).

The solution polymerization process of the present invention employs a stirred tank reactor system comprising one or more stirred polymerization reactors. In general, the reactors should be operated under conditions that achieve thorough mixing of the reactants. In a multiple reactor system, the first polymerization reactor preferably operates at the lower temperature. The residence time of each reactor depends on the design and capacity of the reactor. The catalyst/activator can be fed only to the first reactor or split between the two reactors. In another embodiment, loop reactors and plug flow reactors can be used in the present invention.

The polymer solution is then discharged from the reactor as an effluent stream and the polymerization reaction is typically quenched with a coordinating polar compound to prevent further polymerization. Upon exiting the reactor system, the polymer solution passes through a heat exchanger system and is sent to a devolatilization system and polymer finishing process. The dilute phase and volatiles removed downstream of the liquid phase separation can be recycled as part of the polymerization feed.

The polymer may be recovered from the reactor effluent or mixed effluent by separating the polymer from other components of the effluent. Conventional separation means may be used. For example, the polymer may be recovered from the effluent by coagulation with a non-solvent, such as isopropyl alcohol, acetone, or n-butyl alcohol, or the polymer may be recovered by thermal and vacuum stripping the solvent or other medium with heat or steam. One or more conventional additives, such as antioxidants, may be incorporated into the polymer during the recovery procedure. Other recovery methods, such as the use of a lower critical solution temperature (LCST) followed by devolatilization, are also contemplated.

Suitable diluents/solvents for carrying out the polymerization reaction include non-coordinating inert liquids. In certain embodiments, the reaction mixture for the solution polymerization reaction disclosed herein may include at least one hydrocarbon solvent. Examples include straight and branched chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as those commercially available (Isopar™); halogenated and perhalogenated hydrocarbons, such as perfluoro C ₄ -C ₁₀ alkanes, chlorobenzene, and mixtures thereof; aromatic and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene, ethylbenzene, xylene, and mixtures thereof. Mixtures of any of the aforementioned hydrocarbon solvents may also be used. Suitable solvents include ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In another embodiment, the solvent is not aromatic, and preferably aromatics are present in the solvent at less than 1 weight percent, preferably less than 0.5 weight percent, preferably less than 0 weight percent, based on the weight of the solvent.

Any olefin feed can be polymerized using the polymerization methods and solution polymerization conditions disclosed herein. Suitable olefin feeds can include any C2-C40 alkene, which contains at least one cyclic or substituted cyclic olefin, optionally containing heteroatom substitution, and can be linear or branched, cyclic or non-cyclic, and terminal or non-terminal. In a more specific embodiment, the olefin feed includes _{a C2} - _C20 alkene, particularly a linear alpha olefin, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, or 1-dodecene, in combination with a cyclic olefin, such as, but not _limited to, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclononene, cyclodecene, and 2-norbornene. Other suitable olefin monomers can include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or non-conjugated dienes, polyenes, and vinyl monomers. Non-limiting olefin monomers may also include norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrene, alkyl-substituted styrenes, ethylidene norbornene, and dicyclopentadiene. A single olefin monomer or any mixture of olefin monomers may be polymerized according to the disclosure herein.

In certain embodiments, the cyclic olefin is selected from substituted or unsubstituted _C4 - _C20 cyclic olefins, preferably containing at least one _C4 - _C8 ring structure, hi certain embodiments, the cyclic olefin is cyclopentene or _C1 - _C10 alkyl substituted cyclopentene, provided that preferably the substitution is not on the ^sp2 carbon atom.

In some embodiments, the cyclic olefin is a substituted or unsubstituted _C6 - _C20 polycyclic olefin, including bicyclic olefins, which are cyclic olefins that contain bridged hydrocarbon groups that form multiple rings throughout the structure. Also in some embodiments, the cyclic olefin is norbornene or a _C1 - _C10 alkyl substituted norbornene, provided that the substitution is preferably not on the ^sp2 carbon atom.

Preferred cyclic olefins include cyclopentene and 2-norbornene.

Preferred diolefin monomers useful in the present invention include any hydrocarbon structure (preferably C ₅ -C 30 ) having at least two unsaturated bonds that can be readily incorporated into a polymer to form a crosslinked polymer. Examples of such polyenes include α,ω-dienes (e.g., butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9- _decadiene , 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene) and certain polycyclic alicyclic fused and bridged ring dienes (e.g., tetrahydroindene, divinylbenzene, norbornadiene, methyltetrahydroindene; dicyclopentadiene, divinylbenzene, norbornadiene, methyltetrahydroindene; dicyclopentadiene, divinylbenzene, dicyclopentadiene ... bicyclo-(2.2.1)-hepta-2,5-diene); and alkenyl-, alkylidene-, cycloalkenyl-, and cycloalkylene norbornenes, including, for example, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propentyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, and 5-vinyl-2-norbornene.

Apart from that, dienes are not present in the copolymers produced herein.

Monomer combinations useful herein include ethylene and cyclic olefins, propylene with cyclic olefins; ethylene and propylene with cyclic olefins.

Preferred polymerizations can be carried out at any temperature and/or pressure suitable to obtain the desired polymer. Solution polymerization conditions suitable for use in the polymerization processes disclosed herein include temperatures ranging from about 0°C to about 300°C, or from about 50°C to about 250°C, or from about 70°C to about 200°C, or from about 90°C to about 180°C, or from about 90°C to about 140°C, or from about 120°C to about 140°C. Pressures can range from about 0.1 MPa to about 15 MPa, or from about 0.2 MPa to about 12 MPa, or from about 0.5 MPa to about 10 MPa, or from about 1 MPa to about 7 MPa. Polymerization times (residence times) range up to about 300 minutes, particularly from about 5 minutes to about 250 minutes, or from about 10 minutes to about 120 minutes.

Small amounts of hydrogen, e.g., 1 to 5,000 parts by weight (ppm) based on the total solution fed to the reactor, can be added to one or more of the feed streams of the reactor system to improve control of the melt index and/or molecular weight distribution. In some embodiments, hydrogen can be included in the reaction vessel in a solution polymerization process. According to various embodiments, the concentration of hydrogen gas in the reaction mixture can range from up to about 5,000 ppm, or up to about 4,000 ppm, or up to about 3,000 ppm, or up to about 2,000 ppm, or up to about 1,000 ppm, or up to about 500 ppm, or up to about 400 ppm, or up to about 300 ppm, or up to about 200 ppm, or up to about 100 ppm, or up to about 50 ppm, or up to about 10 ppm, or up to about 1 ppm. In some or other embodiments, hydrogen gas may be present in the reaction vessel at a partial pressure of about 0.007 to 345 kPa, or about 0.07 to 172 kPa, or about 0.7 to 70 kPa. In some embodiments, the process excludes the addition of hydrogen.

In a preferred embodiment, the polymerization is: 1) carried out at a temperature of 100°C or more (preferably 120°C or more, preferably 140°C or more); 2) carried out at a pressure of atmospheric to 18 MPa (preferably 0.35 to 18 MPa, preferably 0.35 to 10 MPa, preferably 0.45 to 6 MPa, preferably 0.5 to 4 MPa); 3) carried out in an aliphatic hydrocarbon solvent (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; preferably, aromatics (such as toluene) are preferably present in the solvent, and are less than 1% by weight, preferably less than 0.5% by weight, preferably less than 0.1% by weight, preferably 0% by weight, based on the weight of the solvent); 4) If used, ethylene is present in the polymerization reactor at a concentration of 6 moles/liter or less). 5) The polymerization preferably occurs in one reaction zone. 6) The productivity of the catalyst compound is 50,000 kg or more of polymer per kg of catalyst (preferably, 100,000 kg or more of polymer per kg of catalyst, 150,000 kg or more of polymer per kg of catalyst, 200,000 kg or more of polymer per kg of catalyst, etc.).

In more specific embodiments, the one or more olefin monomers present in the reaction mixtures disclosed herein include at least one cyclic olefin, optionally ethylene and/or propylene, and optionally one or more alpha olefins, such as butene, hexene, and octene. In even more specific embodiments, the one or more olefin monomers may include a cyclic olefin and ethylene and/or propylene. In even more specific embodiments, the one or more olefin monomers may include ethylene and one or more cyclic olefins, such as cyclopentene and/or 2-norbornene. In even more specific embodiments, the one or more olefin monomers may include propylene and one or more cyclic olefins, such as cyclopentene and/or 2-norbornene.

The molecular weight distribution of polymers produced by solution processes can be advantageously controlled by producing the polymer in multiple reactors that are controlled under different conditions, most often at different temperatures and/or monomer concentrations. These conditions determine the molecular weight and density of the polymer fractions produced. The relative amounts of the different fractions are controlled by adjusting the process conditions in each reactor. Process conditions typically used include the type and concentration of catalyst in each reactor, and the residence time of the reactor. In one embodiment, the polymerization process includes at least two reactors connected in either a series or parallel configuration.

In an embodiment herein, the invention relates to a polymerization process in which a monomer, and optionally a comonomer, is contacted with a catalyst system comprising an activator and at least one catalyst compound, as described above. The catalyst compound and activator can be combined in any order, and are typically combined prior to contact with the monomer. In one embodiment, the catalyst and activator can be fed to the polymerization reactor in the form of a dry powder or slurry, without the need to prepare a homogeneous catalyst solution by dissolving the catalyst in a support solvent.

The polymerization process of the present invention can be carried out in any manner known in the art. Any suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process known in the art can be used. Such processes can be run in batch, semi-batch, or continuous modes. Homogeneous polymerization processes are preferred. (Homogeneous polymerization processes are preferably those in which at least 90% by weight of the product is dissolved in the reaction medium.) In a useful embodiment, the process is a solution process.

A "reaction zone" (also referred to as a "polymerization zone") is a vessel in which polymerization occurs, e.g., a batch reactor. When multiple reactors are used in a series or parallel configuration, each reactor is considered a separate polymerization zone. In multi-stage polymerizations, both in batch and continuous reactors, each polymerization stage is considered a separate polymerization zone. In a preferred embodiment, polymerization occurs in one reaction zone. In one embodiment, multiple reactors are used in the polymerization process.

Other additives may be used, if desired, such as one or more scavengers, hydrogen, aluminum alkyls, silanes, or chain transfer agents (e.g., alkylalumoxanes of the formula _AlR3 or _{ZnR2 ,} where each R is independently a _C1 - _C8 aliphatic group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyloctyl, or an isomer thereof, or diethylzinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof).

The process of the present invention can be used to prepare homopolymers of cyclic olefins, and copolymers of ethylene and cyclic olefins, propylene and cyclic olefins, and can include alpha-olefins to produce polymers having a density of, for example, about 0.900-0.970 g/cm ³ , particularly 0.915-0.965 g/cm ³ . Such polymers can have a melt index, for example, in the range of about 0.1-200 dg/min, particularly in the range of about 0.5-120 dg/min, as measured by the method of ASTM D-1238. The polymers can be produced with narrow or broad molecular weight distribution. For example, the polymers can have a MWD in the range of about 1.5-10, particularly in the range of about 2-7. It is believed that the process of the present invention is particularly useful for producing polymers with narrow molecular distribution.

The process ^of the present invention can be used to prepare cyclic olefin copolymers of ethylene and/or propylene, as well as copolymers ^of cyclic olefins with ethylene and/or propylene and additional alpha-olefins, having a density of, for example, about 0.84 to 0.970 g/cm 3 , particularly 0.88 to 0.965 g/cm 3. Such polymers have a melt index of 0.1 or less, in the range of about 0.5 to 120 dg/min, as measured by the method of ASTM D-1238.

Polyolefin Products The present invention also relates to compositions produced by the methods described herein. The methods described herein can be used to produce polymers and copolymers of cyclic olefins. Polymers that can be prepared include homopolymers of cyclic monomers and copolymers of cyclic olefins with _C2 - _C20 olefins. Polymers that can be prepared herein include copolymers of cyclic olefins and ethylene with any _C4 - _C20 olefin; copolymers of cyclic olefins and propylene with any _C4 - _C20 olefin; copolymers of cyclic olefins, ethylene, and propylene with any _C4 - _C20 olefin.

Preferably, dienes are not present in the polymer compositions produced herein.

In preferred embodiments, the polymer obtained by the methods described herein may contain 0.1 mol% or more of cyclic olefin monomer, or 0.2 mol% or more of cyclic olefin monomer, or 0.5 mol% or more of cyclic olefin monomer, or 1.0 mol% or more of cyclic olefin monomer, or 2.0 mol% or more of cyclic olefin monomer, or 3.0 mol% or more of cyclic olefin monomer, or 5 mol% or more of cyclic olefin monomer, or 10 mol% or more of cyclic olefin monomer, or 15 mol% or more of cyclic olefin monomer, or 20 mol% or more of cyclic olefin monomer, or 30 mol% or more of cyclic olefin monomer, or 40 mol% or more of cyclic olefin monomer, or 50 mol% or more of cyclic olefin monomer, or 60 mol% or more of cyclic olefin monomer, or 70 mol% or more of cyclic olefin monomer, or 80 mol% or more of cyclic olefin monomer, or 90 mol% or more of cyclic olefin monomer, or 100 mol% of cyclic olefin.

Molecular weight (weight average molecular weight (Mw), number average molecular weight (Mn), z-average molecular weight (Mz)) and molecular weight distribution (PDI = MWD = Mw/Mn) (also called the polydispersity (PDI) of the polymer) are measured by gel permeation chromatography against linear polystyrene standards as follows:

In a preferred embodiment, the processes described herein produce copolymers comprising ethylene and a cyclic olefin, where the cyclic olefin is a _C5 to _C20 cyclic olefin, preferably cyclopentene and/or 2-norbornene, the copolymer having a Mn of 3,000 g/mol or more, alternatively 5,000 g/mol or more, alternatively 10,000 g/mol or more, alternatively 50,000 g/mol or more, alternatively 75,000 g/mol or more, alternatively 100,000 g/mol or more, alternatively 200,000 g/mol or more, and having a Mw/Mn between 1.0 to 10, alternatively between 1.5 to 5.0, alternatively between 1.8 to 3.0, and the cyclic olefin content may be from 0.05 to 99 mol%, alternatively 0.1 to 50 mol%, alternatively 0.2 to 40 mol%, alternatively 0.3 to 30 mol%, alternatively 0.5 to 20 mol%. The cyclic olefins may be incorporated through 1,2 bonds (across a double bond) or 1,3 bonds (by rearrangement), or a combination of both.

In a preferred embodiment, the processes described herein produce copolymers comprising ethylene, a cyclic olefin, and one or more additional _C3 - _C12 alpha olefins, where the cyclic olefin is a _C5 - _C20 cyclic olefin, preferably cyclopentene and/or 2-norbornene, and the copolymer has a Mn of 3,000 g/mol or more, alternatively 5,000 g/mol or more, alternatively 10,000 g/mol or more, alternatively 50,000 g/mol or more, alternatively 75,000 g/mol or more, alternatively 100,000 g/mol or more, alternatively 200,000 g/mol or more, and has a Mw/Mn between 1.0 to 10, alternatively between 1.5 to 5.0, alternatively between 1.8 to 3.0, and the cyclic olefin content can be 0.05 to 99 mol%, alternatively 0.1 to up to 50 mol%, alternatively 0.2 to 40 mol%, alternatively 0.3 to 30 mol%, alternatively 0.5 to 20 mol%. The cyclic olefins may be incorporated through 1,2 bonds (across the double backbone) or 1,3 bonds (by rearrangement), or a combination of both.

In some embodiments, the ethylene cyclopentene copolymer has an Mn of about 2,000 to 2,000,000 g/mol, alternatively about 5,000 to 1,500,000 g/mol, alternatively about 10,000 to 1,000,000 g/mol, alternatively about 50,000 to 800,000, alternatively about 100,000 to 500,000 g/mol.

In some embodiments, the ethylene cyclopentene copolymer has a Mw of about 5,000 to 4,000,000 g/mol, alternatively about 10,000 to 3,000,000 g/mol, alternatively about 20,000 to 2,000,000 g/mol, alternatively about 100,000 to 1,500,000 g/mol, alternatively about 200,000 to 1,000,000 g/mol.

In some embodiments, the ethylene cyclopentene copolymer has an Mz of about 100,000 to 10,000,000 g/mol, alternatively about 200,000 to 8,000,000 g/mol, alternatively about 300,000 to 6,000,000 g/mol, alternatively about 400,000 to 3,000,000 g/mol, alternatively about 500,000 to 2,000,000 g/mol.

In some embodiments, the ethylene cyclopentene copolymer has a Mw/Mn of about 1.0 to 10, alternatively about 1.5 to 5.0, alternatively about 1.8 and 3.0, alternatively about 2.0 to 4.0.

In some embodiments, the ethylene cyclopentene copolymer has a cyclopentene content of about 0.05-99 mol%, alternatively about 0.1-50 mol%, alternatively about 0.2-40 mol%, alternatively about 0.3-30 mol%, alternatively about 0.5 mol%-20 mol%. In some embodiments, the ethylene cyclopentene copolymer has a cyclopentene content less than 50 mol%, alternatively less than 45 mol%, alternatively less than 40 mol%.

Cyclopentene monomers may be incorporated through 1,2 bonds (across the double backbone) or 1,3 bonds (by rearrangement), or a combination of both. In some embodiments, the ethylene cyclopentene copolymer has predominantly 1,2 bonds. Preferably, the 1,2 bonds are 90% or more, alternatively 95% or more, alternatively 98% or more, or alternatively 99% or more of the total cyclopentene incorporated into the ethylene backbone. In some embodiments, the ethylene cyclopentene copolymer has 5% or less, alternatively 3% or less, alternatively 2% or less, alternatively 1% or less, or alternatively 0.5% or less of 1,3 bonds. In some embodiments, the triad sequence distribution (ccc, ece, and cce) has a percentage of cccs of 12% or more, alternatively 15% or more, alternatively 20% or more, or alternatively 30% or more, indicating clustering of cyclopentene units. In some embodiments, the triad sequence distribution has an ECE percentage of 86% or less, alternatively 84% or less, alternatively 80% or less, alternatively 70% or less, alternatively 60% or less, or alternatively 50% or less, indicating isolated cyclopentene units.

In some embodiments of the present invention, the ethylene cyclopentene copolymer has a cyclopentene content of greater than 5 mole percent, 1,2-linkages of 90% or more, a ccc sequence distribution of 12% or more, and an ece sequence distribution of 86% or less.

In some embodiments of the present invention, the ethylene cyclopentene copolymer has a cyclopentene content of less than 50 mole percent, 1,2-linkages of 90% or more, a ccc sequence distribution of 12% or more, and an ece sequence distribution of 86% or less.

In a preferred embodiment, the ethylene cyclopentene copolymer is:
a. Mn greater than 5,000 g/mol, alternatively greater than 10,000 g/mol, alternatively greater than 100,000 g/mol, alternatively greater than 150,000 g/mol;
b. Mw greater than 10,000 g/mol, alternatively greater than 20,000 g/mol, alternatively greater than 200,000 g/mol, alternatively greater than 300,000 g/mol;
c. Mw/Mn from about 1 to 10, alternatively from about 1.5 to 5.0, alternatively from about 1.8 to 3.0, alternatively from about 2.0 to 4.0;
d. a cyclopentene content of 0.1 mol% or more and up to 50 mol% or less, alternatively 45 mol% or less;
e. At least about 90% of the total cyclopentene units incorporated into the polymer have cyclopentene 1,2 bonds.

In some embodiments, the ethylene norbornene copolymer has a molecular weight of about 2,000 to 1,500,000 g/mol, alternatively about 5,000 to 1,000,000 g/mol, alternatively about 10,000 to 800,000 g/mol, alternatively about 20,000 to 500,000, alternatively about 30,000 to 300,000 g/mol.

In some embodiments, the ethylene norbornene copolymer has a Mw of about 5,000 to 3,000,000 g/mol, alternatively about 10,000 to 2,000,000 g/mol, alternatively about 20,000 to 1,000,000 g/mol, alternatively about 50,000 to 800,000 g/mol, alternatively about 100,000 to 500,000 g/mol.

In some embodiments, the ethylene norbornene copolymer has an Mz of about 10,000 to 3,000,000 g/mol, alternatively about 20,000 to 2,000,000 g/mol, alternatively about 50,000 to 1,000,000 g/mol, alternatively about 100,000 to 800,000 g/mol, alternatively about 200,000 to 500,000 g/mol.

In some embodiments, the ethylene norbornene copolymer has a Mw/Mn of about 1.0 to 10, alternatively about 1.2 to 5.0, alternatively about 1.5 to 4.0, alternatively about 2.0 to 3.0.

In some embodiments, the ethylene norbornene copolymer has a norbornene content of about 0.1-80 mol%, alternatively about 1-70 mol%, alternatively about 2-60 mol%, alternatively about 2-50 mol%, alternatively about 50 mol%, alternatively about 3-50 mol%, alternatively about 3-45 mol%, alternatively about 4-40 mol%.

In some embodiments, the ethylene norbornene copolymer has a norbornene content of 10 mol% or more, alternatively 20 mol% or more, alternatively 30 mol% or more, alternatively 40 mol% or more, up to an upper limit of 90 mol% or less, alternatively 80 mol% or less.

In some embodiments, the norbornene units in the polymer may be independent, alternating, or block. Preferably, the norbornene units are 10-80% independent, 10-80% alternating, and 1-50% block, with the sum of independent, alternating, and block being 100%. Alternatively, the norbornene units may be 20-80% independent, 20-80% alternating, and 1-45% block.

In some embodiments of the present invention, the ethylene norbornene copolymer has a norbornene content of 20 mol% or more, alternatively 40 mol% or more, alternatively 45 mol% or more, alternatively 50 mol% or more, alternatively 60 mol% or more, or alternatively 70 mol% or more.

In some embodiments, the ethylene norbornene copolymer has a norbornene content of about 10 mol% to about 90 mol%, alternatively about 15 mol% to about 80 mol%, alternatively about 20 mol% to about 70 mol%, alternatively about 20 mol% to about 60 mol%.

In some embodiments, the ethylene norbornene copolymer has a Tg (°C) of 30°C or more, alternatively 40°C or more, alternatively 50°C or more, alternatively 60°C or more, up to and including 200°C.

In a preferred embodiment, the ethylene norbornene copolymer is:
a. Mn greater than 50,000 g/mol, alternatively greater than 100,000 g/mol, alternatively greater than 150,000 g/mol, alternatively greater than 200,000 g/mol;
b. Mw greater than 100,000 g/mol, alternatively greater than 200,000 g/mol, alternatively greater than 300,000 g/mol, alternatively greater than 400,000 g/mol;
c. Mw/Mn from about 1.2 to 5.0, alternatively from about 1.5 to 4.0, alternatively from about 2.0 to 3.0;
d. a norbornene content of 20 mol% or more and 80 mol% or less;
e. 10-80% independent, 10-80% alternating, and 1-50% blocked norbornene units, the total of independent, alternating, and blocked being 100%;
has.

In a preferred embodiment, the process described herein produces a copolymer comprising propylene and a cyclic olefin, where the cyclic olefin is a _C5 to _C20 cyclic olefin, preferably cyclopentene and/or 2-norbornene, the copolymer having a Mn of 3,000 g/mol or more, alternatively 5,000 g/mol or more, alternatively 10,000 g/mol or more, alternatively 50,000 g/mol or more, alternatively 75,000 g/mol or more, alternatively 100,000 g/mol or more, having a Mw/Mn of 1.0 to 10, alternatively 1.5 to 5.0, alternatively 1.8 to 3.0, and having a cyclic olefin content of 0.05 to 99 mol%, alternatively 0.1 to 50 mol%, alternatively 0.2 to 40 mol%, alternatively 0.3 to 30 mol%, alternatively 0.5 to 20 mol%. The cyclopentene may be incorporated through 1,2 or 1,3 bonds or a combination of both.

In a preferred embodiment, the methods described herein comprise propylene and a cyclic olefin, optionally further comprising one or more additional _C4 to _C12 alpha olefins, where the cyclic olefin is a _C5 to _C20 cyclic olefin, preferably cyclopentene and/or 2-norbornene, and the copolymer has a Mn of 3,000 g/mol or more, alternatively 5,000 g/mol or more, alternatively 10,000 g/mol or more, alternatively 50,000 g/mol or more, alternatively 75,000 g/mol or more, alternatively 100,000 g/mol or more, and a Mw/Mn of 1.0 to 10, alternatively 1.5 to 5.0, alternatively 1.8 to 3.0, and a cyclic olefin content of 0.05 to 99 mol%, alternatively 0.1 to 50 mol%, alternatively 0.2 to 40 mol%, alternatively 0.3 to 30 mol%, alternatively 0.5 to 20 mol%. The cyclopentene may be incorporated through 1,2 bonds or 1,3 bonds or a combination of both.

In some embodiments, the propylene cyclopentene copolymer has an Mn of about 1,000 to 1,000,000 g/mol, alternatively about 2,000 to 800,000 g/mol, alternatively about 3,000 to 500,000 g/mol, alternatively about 4,000 to 100,000, alternatively about 5,000 to 50,000 g/mol.

In some embodiments, the propylene cyclopentene copolymer has a Mw of about 2,000 to 2,000,000 g/mol, alternatively about 4,000 to 1,500,000 g/mol, alternatively about 5,000 to 2,000,000 g/mol, alternatively about 8,000 to 500,000 g/mol, alternatively about 10,000 to 200,000 g/mol.

In some embodiments, the propylene cyclopentene copolymer has an Mz of about 5,000 to 4,000,000 g/mol, alternatively about 10,000 to 2,000,000 g/mol, alternatively about 20,000 to 1,000,000 g/mol, alternatively about 25,000 to 500,000 g/mol, alternatively about 30,000 to 200,000 g/mol.

In some embodiments, the propylene cyclopentene copolymer has a Mw/Mn of about 1.0 to 10, alternatively about 1.5 to 5.0, alternatively about 1.8 to 3.0, alternatively about 2.0 to 4.0.

In some embodiments, the propylene cyclopentene copolymer has a cyclopentene content of about 0.05-99 mol%, alternatively about 0.1-50 mol%, alternatively about 0.2-40 mol%, alternatively about 0.3-30 mol%, alternatively about 0.5-20 mol%, alternatively about 1.0 mol% to about 10 mol%. The cyclopentene monomers may be incorporated through 1,2 bonds (across the double bond) or 1,3 bonds (by rearrangement), or a combination of both. In some embodiments, the propylene cyclopentene copolymer has predominantly 1,2 bonds. Preferably, the 1,2 bonds are 90% or more, alternatively 95% or more, alternatively 98% or more, alternatively 99% or more of the total cyclopentene incorporated into the propylene backbone. In some embodiments, the propylene cyclopentene copolymer has 5% or less, alternatively 3% or less, alternatively 2% or less, alternatively 1% or less, alternatively 0.5% or less of 1,3 bonds.

In a preferred embodiment, the propylene cyclopentene copolymer is:
a. Mn greater than 3,000 g/mol, alternatively greater than 5,000 g/mol, alternatively greater than 10,000 g/mol;
b. Mw greater than 6,000 g/mol, alternatively greater than 10,000 g/mol, alternatively greater than 20,000 g/mol;
c. Mw/Mn from about 1 to 10, alternatively from about 1.5 to 5.0, alternatively from about 1.8 to 3.0, alternatively from about 2.0 to 4.0;
d. a cyclopentene content of 0.1 mol% or more and up to 50 mol% or less, alternatively 45 mol% or less;
e. greater than about 90% of the total cyclopentene units incorporated into the polymer are cyclopentene 1,2 bonds;
has.

In some embodiments, the propylene norbornene copolymer has an Mn of about 1,000 to 1,000,000 g/mol, alternatively about 2,000 to 800,000 g/mol, alternatively about 3,000 to 500,000 g/mol, alternatively about 4,000 to 200,000, alternatively about 5,000 to 100,000 g/mol.

In some embodiments, the propylene norbornene copolymer has a Mw of about 2,000 to 2,000,000 g/mol, alternatively about 4,000 to 1,500,000 g/mol, alternatively about 5,000 to 1,000,000 g/mol, alternatively about 8,000 to 500,000 g/mol, alternatively about 10,000 to 300,000 g/mol.

In some embodiments, the propylene norbornene copolymer has an Mz of about 4,000 to 3,000,000 g/mol, alternatively about 5,000 to 2,000,000 g/mol, alternatively about 6,000 to 1,500,000 g/mol, alternatively about 10,000 to 800,000 g/mol, alternatively about 10,000 to 500,000 g/mol.

In some embodiments, the propylene norbornene copolymer has a Mw/Mn of about 1.0 to 10, alternatively about 1.2 to 5.0, alternatively about 1.5 and 4.0, alternatively about 2.0 to 3.0.

In some embodiments, the propylene norbornene copolymer has a norbornene content of about 0.1-60 mol%, alternatively about 1-50 mol%, alternatively about 2-40 mol%, alternatively about 3-35 mol%, alternatively about 4-30 mol%.

In some embodiments, the propylene norbornene copolymer has a Tm (°C) of about 90 to about 130°C. In other embodiments, the propylene norbornene copolymer is amorphous and does not exhibit polymer crystallinity.

In a preferred embodiment, the propylene norbornene copolymer is
a. Mn greater than 3,000 g/mol, alternatively greater than 5,000 g/mol, alternatively greater than 10,000 g/mol;
b. Mw greater than 6,000 g/mol, alternatively greater than 10,000 g/mol, alternatively greater than 20,000 g/mol;
c. Mw/Mn from about 1.2 to 5.0, alternatively from about 1.5 to 4.0, alternatively from about 2.0 to 3.0;
d. The norbornene content is 1 mol % or more and 50 mol % or less.

In some embodiments, the polymer produced is a homopolymer of cyclopentene (polycyclopentene) having an Mn of about 100-5,000 g/mol, alternatively about 200-2,000 g/mol, alternatively about 250-1,200 g/mol, alternatively about 300-1,000 g/mol.

In some embodiments, the polymer produced is a homopolymer of cyclopentene having a Mw of about 200-10,000 g/mol, alternatively about 300-5,000 g/mol, alternatively about 350-2,000 g/mol, alternatively about 300-1,000 g/mol.

In some embodiments, the polymer produced is a homopolymer of cyclopentene having an Mz of about 400-20,000 g/mol, alternatively about 500-10,000 g/mol, alternatively about 600-5,000 g/mol, alternatively about 700-1,000 g/mol.

In some embodiments, the Mn of the polycyclopentene is less than 1000 g/mol, alternatively less than 800 g/mol, alternatively less than 600 g/mol, alternatively less than 500 g/mol, and the Mn is 200 g/mol or more, alternatively 250 g/mol or more, alternatively 300 g/mol or more.

In preferred embodiments, the polymers produced herein have a unimodal or multimodal molecular weight distribution as determined by gel permeation chromatography (GPC). "Unimodal" means that the GPC chromatograph has one peak or inflection point. "Multimodal" means that the GPC chromatograph has at least two peaks or inflection points. An inflection point is a point where the sign of the second derivative of the curve changes (e.g., from negative to positive or from negative to positive).

Blends In another embodiment, the polymer compositions produced herein are combined with one or more additional polymers before being formed into a film, molded part, or other article. Other useful polymers include polyethylene, polypropylene, random copolymers of propylene and ethylene, and/or butene, and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethyl methacrylate or other polymers polymerizable by high pressure free radical processes, polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resins, ethylene propylene rubber (EPR), vulcanized EPR, EPDM, block copolymers, styrenic block copolymers, polyamides, polycarbonates, PET resins, crosslinked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetals, polyvinylidene fluoride, polyethylene glycol, and/or polyisobutylene.

In a preferred embodiment, the polymer produced herein is present in said blend at 10-99% by weight, preferably 20-95% by weight, even more preferably at least 30-90% by weight, even more preferably at least 40-90% by weight, even more preferably at least 50-90% by weight, even more preferably at least 60-90% by weight, even more preferably at least 70-90% by weight, based on the weight of the polymer in the blend.

The above blends can be made by mixing the polymer of the present invention with one or more polymers (as described above), by connecting reactors in series to make a reactor blend, or by using two or more catalysts to produce multiple polymer species in the same reactor. The polymers can be mixed together prior to entering the extruder or can be mixed in the extruder. Alternatively, the above blends can be made by mixing the polymer of the present invention with one or more polymers (as described above) and connecting reactors in parallel or series to make a reactor blend.

The blends can be formed using conventional equipment and methods, such as by dry blending the individual components followed by melt mixing in a mixer, or by mixing the components together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin screw extruder, which may include compounding extruders and side arm extruders used immediately downstream of the polymerization process, which may include blending resin powders or pellets in the hopper of a film extruder. Additionally, additives can be included in the blend, one or more components of the blend, and/or in the product (such as a film) formed from the blend, as desired. Such additives are well known in the art and may include, for example, the following: antioxidants (e.g., hindered phenols such as IRGANOX ^™ 1010 or IRGANOX ^™ 1076 available from BASF); phosphites (e.g., IRGAFOS™ 168 available from BASF); antiblocking additives; tackifiers such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosin; ultraviolet light stabilizers; heat stabilizers; antiblocking agents; release agents; antistatic agents; pigments; colorants; dyes; waxes; silicas; fillers; talc, and the like.

Films , specifically any of the aforementioned polymers, such as the aforementioned polymers or blends thereof, can be used in a variety of end-use applications. Such applications include, for example, monolayer or multilayer blown, extruded, and/or shrink films. These films can be formed by any number of well-known extrusion or coextrusion techniques, such as blown bubble film processing techniques, in which the composition is extruded in a molten state through an annular die and then expanded to form a tubular blown film before being cooled. It is then axially slit and unfolded to form a flat film. The film can subsequently be unstretched, uniaxially stretched, or biaxially stretched to the same or different extents. One or more layers of the film can be oriented to the same or different extents in the transverse and/or longitudinal directions. The uniaxial orientation can be obtained using typical cold or hot stretching methods. The biaxial orientation can be achieved using a tenter frame apparatus or a double bubble process, and can be achieved before or after the individual layers are brought together. For example, a polyethylene layer can be extrusion coated or laminated onto an oriented polypropylene layer, or polyethylene and polypropylene can be coextruded together into a film and then oriented. Similarly, oriented polypropylene can be laminated to oriented polyethylene, or oriented polyethylene can be coated onto polypropylene, and optionally the combination can be further oriented. Typically, the film is oriented in the machine direction (MD) by a ratio of up to 15, preferably 5-7, and in the transverse direction (TD) by a ratio of up to 15, preferably 7-9. In another embodiment, the film is oriented to the same extent in both the MD and TD directions.

The thickness of the film will vary depending on the application. However, typically a film thickness of 1-50 μm is suitable. Packaging films are usually 10-50 μm thick. The sealing layer is typically 0.2-50 μm thick. There may be a sealing layer on both the inner and outer surfaces of the film, or the sealing layer may be present only on the inner or outer surface.

In another embodiment, one or more layers can be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave. In a preferred embodiment, one or both of the surface layers are modified by corona treatment.

Any of the aforementioned polymers and compositions, in combination with any additives (see, for example, U.S. Patent Application Publication No. 2016/0060430, paragraphs [0082]-[0093]), can be used in a variety of end-use applications. Such end-use applications can be produced by methods known in the art. End-use applications include polymer products and products having specific end-use applications. Exemplary end-use applications can be films, film-based products, diaper backsheets, house wraps, wire and cable coating compositions, articles formed by molding techniques, such as injection or blow molding, extrusion coating, foaming, casting, and combinations thereof. End-use applications also include products made from films, such as bags, packaging, personal care films, pouches, medical products, such as medical films and intravenous (IV) bags.

Lubricants and Viscosity Modifiers The present invention also provides a lubricant composition comprising a blend of the ethylene-cyclic monomer copolymer described herein and a lubricating oil. The concentration of the ethylene cyclic monomer copolymer in the lubricating oil is 5% by weight or less. The branched ethylene copolymer has a shear stability index (30 cycles) in the lubricating oil of about 10% to about 60% and a kinematic viscosity at 100° C. of about 5 cSt to about 20 cSt. The shear stability index (SSI) is determined according to ASTM D6278 at 30 cycles using a Kurt Orbahn diesel injector. The kinematic viscosity (KV) is measured according to ASTM D445.

［式中：
Ｍは、３、４、５、または６族の遷移金属またはランタニドであり；
ＥおよびＥ’は、それぞれ独立して、Ｏ、ＳまたはＮＲ^９であり、ここに、Ｒ^９は、独立して、水素、Ｃ_１～Ｃ_４０ヒドロカルビル、Ｃ_１～Ｃ_４０置換ヒドロカルビルまたはヘテロ原子含有基であり；
Ｑは、金属Ｍと配位結合を形成する、１４、１５、または１６族の原子であり、
Ａ^１ＱＡ^１’は、３原子架橋により、Ａ^２とＡ^２’を連結する、４～４０個の非水素原子を含むヘテロサイクリックルイス塩基の一部であり、ここに、Ｑは、３原子架橋の中心原子であり、Ａ^１およびＡ^１’は、独立して、Ｃ、Ｎ、またはＣ（Ｒ^２２）であり、Ｒ^２２は、水素、Ｃ_１～Ｃ_２０ヒドロカルビル、Ｃ_１～Ｃ_２０置換ヒドロカルビルから選択され；

は、２原子架橋によりＡ^１とＥ結合アリール基を連結する、２～４０個の非水素原子を含む二価の基であり；

は、２原子架橋によりＡ^１’とＥ’結合アリール基を連結する、２～４０個の非水素原子を含む二価の基であり；
Ｌは、ルイス塩基であり；
Ｘは、アニオン配位子であり；
ｎは１、２または３であり；
ｍは０、１、または２であり；
ｎ＋ｍは４以下であり；
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^１’、Ｒ^２’、Ｒ^３’、およびＲ^４’は、それぞれ独立して、水素、Ｃ_１～Ｃ_４０ヒドロカルビル、Ｃ_１～Ｃ_４０置換ヒドロカルビル、ヘテロ原子、またはヘテロ原子含有基であり；
Ｒ^１とＲ^２、Ｒ^２とＲ^３、Ｒ^３とＲ^４、Ｒ^１’とＲ^２’、Ｒ^２’とＲ^３’、Ｒ^３’とＲ^４’のうちの１つまたは複数は、結合して、それぞれが５、６、７、または８個の環原子を有する、１つまたは複数の、置換ヒドロカルビル環、非置換ヒドロカルビル環、置換ヘテロサイクリック環、または非置換ヘテロサイクリック環を形成してもよく、ここに、環上の置換は、結合して追加の環を形成してもよく；
任意の２つのＬ基は、結合して、二座ルイス塩基を形成してもよく；
Ｘ基は、Ｌ基に結合して、モノアニオン性二座基を形成してもよく；
任意の２つのＸ基は、結合して、ジアニオン配位子を形成してもよい。］
により表される触媒化合物を含む触媒系と接触させることを含む、重合方法。
２． 前記触媒化合物は、式（ＩＩ）：

［式中：
Ｍは、３、４、５、または６族の遷移金属またはランタニドであり；
ＥおよびＥ’は、それぞれ独立して、Ｏ、ＳまたはＮＲ^９であり、ここに、Ｒ^９は、独立して、水素、Ｃ_１～Ｃ_４０ヒドロカルビル、Ｃ_１～Ｃ_４０置換ヒドロカルビルまたはヘテロ原子含有基であり；
Ｌは、それぞれ独立して、ルイス塩基であり；
ｎは１、２または３であり；
ｍは０、１、または２であり；
ｎ＋ｍは４以下であり；
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^１’、Ｒ^２’、Ｒ^３’、およびＲ^４’は、それぞれ独立して、水素、Ｃ_１～Ｃ_４０ヒドロカルビル、Ｃ_１～Ｃ_４０置換ヒドロカルビル、ヘテロ原子、またはヘテロ原子含有基であり；
Ｒ^１とＲ^２、Ｒ^２とＲ^３、Ｒ^３とＲ^４、Ｒ^１’とＲ^２’、Ｒ^２’とＲ^３’、Ｒ^３’とＲ^４’の１つまたは複数は、結合して、それぞれが５、６、７、または８個の環原子を有する、１つまたは複数の、置換ヒドロカルビル環、非置換ヒドロカルビル環、置換ヘテロサイクリック環、または非置換ヘテロサイクリック環を形成してもよく、ここに、環上の置換は、結合して追加の環を形成してもよく；
任意の２つのＬ基は、結合して、二座ルイス塩基を形成してもよく；
Ｘ基は、Ｌ基に結合して、モノアニオン性二座基を形成してもよく；
任意の２つのＸ基は、結合して、ジアニオン配位子を形成してもよく；
Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^５’、Ｒ^６’、Ｒ^７’、Ｒ^８’、Ｒ^１０、Ｒ^１１、およびＲ^１２は、それぞれ独立して、水素、Ｃ_１～Ｃ_４０ヒドロカルビル、Ｃ_１～Ｃ_４０置換ヒドロカルビル、ヘテロ原子またはヘテロ原子含有基であり；
Ｒ^５とＲ^６、Ｒ^６とＲ^７、Ｒ^７とＲ^８、Ｒ^５’とＲ^６’、Ｒ^６’とＲ^７’、Ｒ^７’とＲ^８’、Ｒ^１０とＲ^１１、またはＲ^１１とＲ^１２の１つまたは複数は、結合して、それぞれが５、６、７、または８個の環原子を有する、１つまたは複数の、置換ヒドロカルビル環、非置換ヒドロカルビル環、置換ヘテロサイクリック環、または非置換ヘテロサイクリック環を形成してもよく、ここに、環上の置換は、結合して追加の環を形成してもよい。］
により表される、項１に記載の方法。
３． Ｍは、Ｈｆ、ＺｒまたはＴｉである、項１または２に記載の方法。
４．
ＥおよびＥ’は、それぞれＯである、項１、２または３に記載の方法。
５． Ｒ^１およびＲ^１’は、それぞれ独立して、Ｃ_４～Ｃ_４０第三級ヒドロカルビル基である、項１、２、３、または４に記載の方法。
６． Ｒ^１およびＲ^１’は、それぞれ独立して、Ｃ_４～_Ｃ４０環式第三級ヒドロカルビル基である、項１、２、３、または４に記載の方法。
７． Ｒ^１およびＲ^１’は、それぞれ独立して、Ｃ_４～Ｃ_４０多環式第三級ヒドロカルビル基である、項１、２、３、または４に記載の方法。
８． Ｘは、それぞれ独立して、１～２０個の炭素原子を有する置換または非置換のヒドロカルビルラジカル、水素化物、アミド、アルコキシド、スルフィド、リン化物、ハロゲン化物、およびそれらの組み合わせ（２つのＸは、縮合環または環系の一部を形成してもよい）である、項１～７のいずれか１項に記載の方法。
９． Ｌは、それぞれ独立して、エーテル、チオエーテル、アミン、ホスフィン、エチルエーテル、テトラヒドロフラン、ジメチルスルフィド、トリエチルアミン、ピリジン、アルケン、アルキン、アレン、およびカルベン、ならびにそれらの組み合わせ（所望により、２つ以上のＬは、縮合環または環系の一部を形成してもよい）である、項１～８のいずれか１項に記載の方法。
１０． ＭはＺｒまたはＨｆであり、Ｑは窒素であり、Ａ^１およびＡ^１’の両方は炭素であり、ＥおよびＥ^’の両方は酸素であり、Ｒ^１およびＲ^１’の両方はＣ_４～Ｃ_２０環状第三級アルキルである、項１に記載の方法。
１１． ＭはＺｒまたはＨｆであり、Ｑは窒素であり、Ａ^１およびＡ^１’の両方は炭素であり、ＥおよびＥ^’の両方は酸素であり、Ｒ^１およびＲ^１’の両方はアダマンタン－１－イルまたは置換アダマンタン－１－イルである、項１に記載の方法。
１２． ＭはＺｒまたはＨｆであり、Ｑは窒素であり、Ａ^１およびＡ^１’の両方は炭素であり、ＥおよびＥ^’の両方は酸素であり、Ｘはメチルまたはクロロであり、ｎは２である、項１に記載の方法。
１３． Ｑは窒素であり、Ａ^１およびＡ^１’の両方は炭素であり、Ｒ^１およびＲ^１’の両方は水素であり、ＥおよびＥ^’の両方はＮＲ^９であり、Ｒ^９はＣ_１～Ｃ_４０ヒドロカルビル、Ｃ_１～Ｃ_４０置換ヒドロカルビル、またはヘテロ原子含有基から選択される、項１に記載の方法。
１４． Ｑは炭素であり、Ａ^１およびＡ^１’の両方は窒素であり、ＥおよびＥ^’の両方は酸素である、項１に記載の方法。
１５． Ｑは炭素であり、Ａ^１は窒素であり、Ａ^１’はＣ（Ｒ^２２）であり、ＥおよびＥ^’の両方は酸素であり、Ｒ^２２は水素、Ｃ_１～Ｃ_２０ヒドロカルビル、またはＣ_１～Ｃ_２０置換ヒドロカルビルから選択される、項１に記載の方法。
１６． ヘテロサイクリックルイス塩基は、下記式：

［式中、Ｒ^２３は、それぞれ独立して、水素、Ｃ_１～Ｃ_２０アルキル、およびＣ_１～Ｃ_２０置換アルキルから選択される。］
により表される基から選択される、項１に記載の方法。
１７． ＭはＺｒまたはＨｆであり、ＥおよびＥ^’の両方は酸素であり、Ｒ^１およびＲ^１’の両方はＣ_４～Ｃ_２０環状第三級アルキルである、項２に記載の方法。
１８． ＭはＺｒまたはＨｆであり、ＥおよびＥ^’の両方は酸素であり、Ｒ^１およびＲ^１’の両方はアダマンタン－１－イルまたは置換アダマンタン－１－イルである、項２に記載の方法。
１９． ＭはＺｒまたはＨｆであり、ＥおよびＥ^’の両方は酸素であり、Ｒ^１、Ｒ^１’、Ｒ^３およびＲ^３’のそれぞれはアダマンタン－１－イルまたは置換アダマンタン－１－イルである、項２に記載の方法。
２０． ＭはＺｒまたはＨｆであり、ＥおよびＥ^’の両方は酸素であり、Ｒ^１およびＲ^１’の両方はＣ_４～_Ｃ２０環状第三級アルキルであり、Ｒ^７およびＲ^７’の両方はＣ_１～Ｃ_２０アルキルである、項２に記載の方法。
２１． ＭはＺｒまたはＨｆであり、ＥおよびＥ^’の両方はＯであり、Ｒ^１およびＲ^１’の両方はＣ_４～Ｃ_２０環状第三級アルキルであり、Ｒ^７およびＲ^７’の両方はＣ_１～Ｃ_２０アルキルである、項２に記載の方法。
２２． ＭはＺｒまたはＨｆであり、ＥおよびＥ^’の両方はＯであり、Ｒ^１およびＲ^１’の両方はＣ_４～Ｃ_２０環状第三級アルキルであり、Ｒ^７およびＲ^７’の両方はＣ_１～Ｃ_３アルキルである、項２に記載の方法。
２３． 触媒化合物は、下記式：

により表される基の１つまたは複数である、項１に記載の方法。
２４． 触媒化合物は、下記式：

により表される基の１つまたは複数である、項１に記載の方法。
２５． 活性化剤は、アルモキサンまたは非配位アニオンを含む、項１～２４のいずれか１項に記載の方法。
２６． 活性化剤は、非芳香族炭化水素溶媒に可溶である、項１～２４のいずれか１項に記載の方法。
２７． 触媒系は、芳香族溶媒を含まない、項１～２４のいずれか１項に記載の方法。
２８． 活性化剤は、式：

［式中、Ｚは（Ｌ－Ｈ）または還元可能なルイス酸であり、Ｌは中性ルイス塩基であり；Ｈは水素であり；（Ｌ－Ｈ）^＋はブレンステッド酸であり；Ａ^ｄ－は、電荷ｄ－を有する非配位アニオンであり；ｄは１～３の整数である。］
により表される、項１～２７のいずれか１項に記載の方法。
２９． 活性化剤は、式：

［式中：
Ｅは、窒素またはリンであり；
ｄは、１、２、または３であり；ｋは、１、２、または３であり；ｎは、１、２、３、４、５、または６であり；ｎ－ｋ＝ｄであり；
Ｒ^１’、Ｒ^２’、およびＲ^３’は、独立して、１つまたは複数の、アルコキシ基、シリル基、ハロゲン原子、またはハロゲン含有基により置換されていてもよい、Ｃ_１～Ｃ_５０ヒドロカルビル基であり；
ここに、Ｒ^１’、Ｒ^２’、およびＲ^３’は、合わせて１５個以上の炭素原子を含み；
Ｍｔは、元素の周期表の第１３族から選択された元素であり；
Ｑは、それぞれ独立して、水素化物、架橋または非架橋ジアルキルアミド、ハロゲン化物、アルコキシド、アリールオキシド、ヒドロカルビル、置換ヒドロカルビル、ハロカルビル、置換ハロカルビル、またはハロ置換ヒドロカルビル基である。］
により表される、項１～２７のいずれか１項に記載の方法。
３０． 活性化剤は、式：

［式中、Ａ^ｄ－は、電荷ｄ－を有する非配位アニオンであり；ｄは１～３の整数であり、（Ｚ）_ｄ ^＋は、

の１つまたは複数により表される。］
により表される、項１～２７のいずれか１項に記載の方法。
３１． 活性化剤は：
Ｎ－メチル－４－ノナデシル－Ｎ－オクタデシルベンゼンアミニウムテトラキス（ペンタフルオロフェニル）ボレート、
Ｎ－メチル－４－ノナデシル－Ｎ－オクタデシルベンゼンアミニウムテトラキス（パーフルオロナフタレン－２－イル）ボレート、
ジオクタデシルメチルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、
ジオクタデシルメチルアンモニウムテトラキス（パーフルオロナフタレン－２－イル）ボレート、
Ｎ，Ｎ－ジメチルアニリニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリメチルアンモニウムテトラキス（パーフルオロナフタレン－２－イル）ボレート、
トリエチルアンモニウムテトラキス（パーフルオロナフタレン－２－イル）ボレート、
トリプロピルアンモニウムテトラキス（パーフルオロナフタレン－２－イル）ボレート、
トリ（ｎ－ブチル）アンモニウムテトラキス（パーフルオロナフタレン－２－イル）ボレート、
トリ（ｔ－ブチル）アンモニウムテトラキス（パーフルオロナフタレン－２－イル）ボレート、
Ｎ，Ｎ－ジメチルアニリニウムテトラキス（パーフルオロナフタレン－２－イル）ボレート、
Ｎ，Ｎ－ジエチルアニリニウムテトラキス（パーフルオロナフタレン－２－イル）ボレート、
Ｎ，Ｎ－ジメチル－（２，４，６－トリメチルアニリニウム）テトラキス（パーフルオロナフタレン－２－イル）ボレート、
トロピリウムテトラキス（パーフルオロナフタレン－２－イル）ボレート、
トリフェニルカルベニウムテトラキス（パーフルオロナフタレン－２－イル）ボレート、
トリフェニルホスホニウムテトラキス（パーフルオロナフタレン－２－イル）ボレート、
トリエチルシリリウムテトラキス（パーフルオロナフタレン－２－イル）ボレート、
ベンゼン（ジアゾニウム）テトラキス（パーフルオロナフタレン－２－イル）ボレート、
トリメチルアンモニウムテトラキス（パーフルオロビフェニル）ボレート、
トリエチルアンモニウムテトラキス（パーフルオロビフェニル）ボレート、
トリプロピルアンモニウムテトラキス（パーフルオロビフェニル）ボレート、
トリ（ｎ－ブチル）アンモニウムテトラキス（パーフルオロビフェニル）ボレート、
トリ（ｔ－ブチル）アンモニウムテトラキス（パーフルオロビフェニル）ボレート、
Ｎ，Ｎ－ジメチルアニリニウムテトラキス（パーフルオロビフェニル）ボレート、
Ｎ，Ｎ－ジエチルアニリニウムテトラキス（パーフルオロビフェニル）ボレート、
Ｎ，Ｎ－ジメチル－（２，４，６－トリメチルアニリニウム）テトラキス（パーフルオロビフェニル）ボレート、
トロピリウムテトラキス（パーフルオロビフェニル）ボレート、
トリフェニルカルベニウムテトラキス（パーフルオロビフェニル）ボレート、
トリフェニルホスホニウムテトラキス（パーフルオロビフェニル）ボレート、
トリエチルシリリウムテトラキス（パーフルオロビフェニル）ボレート、
ベンゼン（ジアゾニウム）テトラキス（パーフルオロビフェニル）ボレート、
［４－ｔ－ブチル－ＰｈＮＭｅ_２Ｈ］［（Ｃ_６Ｆ_３（Ｃ_６Ｆ_５）_２）_４Ｂ］、
トリメチルアンモニウムテトラフェニルボレート、
トリエチルアンモニウムテトラフェニルボレート、
トリプロピルアンモニウムテトラフェニルボレート、
トリ（ｎ－ブチル）アンモニウムテトラフェニルボレート、
トリ（ｔ－ブチル）アンモニウムテトラフェニルボレート、
Ｎ，Ｎ－ジメチルアニリニウムテトラフェニルボレート、
Ｎ，Ｎ－ジエチルアニリニウムテトラフェニルボレート、
Ｎ，Ｎ－ジメチル－（２，４，６－トリメチルアニリニウム）テトラフェニルボレート、
トロピリウムテトラフェニルボレート、
トリフェニルカルベニウムテトラフェニルボレート、
トリフェニルホスホニウムテトラフェニルボレート、
トリエチルシリリウムテトラフェニルボレート、
ベンゼン（ジアゾニウム）テトラフェニルボレート、
トリメチルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリエチルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリプロピルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリ（ｎ－ブチル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリ（ｓｅｃ－ブチル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、
Ｎ，Ｎ－ジメチルアニリニウムテトラキス（ペンタフルオロフェニル）ボレート、
Ｎ，Ｎ－ジエチルアニリニウムテトラキス（ペンタフルオロフェニル）ボレート、
Ｎ，Ｎ－ジメチル－（２，４，６－トリメチルアニリニウム）テトラキス（ペンタフルオロフェニル）ボレート、
トロピリウムテトラキス（ペンタフルオロフェニル）ボレート、
トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリフェニルホスホニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリエチルシリリウムテトラキス（ペンタフルオロフェニル）ボレート、
ベンゼン（ジアゾニウム）テトラキス（ペンタフルオロフェニル）ボレート、
トリメチルアンモニウムテトラキス－（２，３，４，６－テトラフルオロフェニル）ボレート、
トリエチルアンモニウムテトラキス－（２，３，４，６－テトラフルオロフェニル）ボレート、
トリプロピルアンモニウムテトラキス－（２，３，４，６－テトラフルオロフェニル）ボレート、
トリ（ｎ－ブチル）アンモニウムテトラキス－（２，３，４，６－テトラフルオロ－フェニル）ボレート、
ジメチル（ｔ－ブチル）アンモニウムテトラキス－（２，３，４，６－テトラフルオロフェニル）ボレート、
Ｎ，Ｎ－ジメチルアニリニウムテトラキス－（２，３，４，６－テトラフルオロフェニル）ボレート、
Ｎ，Ｎ－ジエチルアニリニウムテトラキス－（２，３，４，６－テトラフルオロフェニル）ボレート、
Ｎ，Ｎ－ジメチル－（２，４，６－トリメチルアニリニウム）テトラキス－（２，３，４，６－テトラフルオロフェニル）ボレート、
トロピリウムテトラキス－（２，３，４，６－テトラフルオロフェニル）ボレート、
トリフェニルカルベニウムテトラキス－（２，３，４，６－テトラフルオロフェニル）ボレート、
トリフェニルホスホニウムテトラキス－（２，３，４，６－テトラフルオロフェニル）ボレート、
トリエチルシリリウムテトラキス－（２，３，４，６－テトラフルオロフェニル）ボレート、
ベンゼン（ジアゾニウム）テトラキス－（２，３，４，６－テトラフルオロフェニル）ボレート、
トリメチルアンモニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
トリエチルアンモニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
トリプロピルアンモニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
トリ（ｎ－ブチル）アンモニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
トリ（ｔ－ブチル）アンモニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
Ｎ，Ｎ－ジメチルアニリニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
Ｎ，Ｎ－ジエチルアニリニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
Ｎ，Ｎ－ジメチル－（２，４，６－トリメチルアニリニウム）テトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
トロピリウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
トリフェニルカルベニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
トリフェニルホスホニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
トリエチルシリリウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
ベンゼン（ジアゾニウム）テトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
ジ－（ｉ－プロピル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、
ジシクロヘキシルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリ（ｏ－トリル）ホスホニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリ（２，６－ジメチルフェニル）ホスホニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリフェニルカルベニウムテトラキス（パーフルオロフェニル）ボレート、
１－（４－（トリス（ペンタフルオロフェニル）ボレート）－２，３，５，６－テトラフルオロフェニル）ピロリジニウム、
テトラキス（ペンタフルオロフェニル）ボレート、
４－（トリス（ペンタフルオロフェニル）ボレート）－２，３，５，６－テトラフルオロピリジン、および
トリフェニルカルベニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート）
の１つまたは複数の１つまたは複数である、項１～２７のいずれか１項に記載の方法。
３２． 溶液法である、項１～３１のいずれか１項に記載の方法。
３３． 約８０℃～約３００℃の温度、約０．３５ＭＰａ～約１０ＭＰａの範囲の圧力、および３００分以下の滞留時間で行われる、項１～３２のいずれか１項に記載の方法。
３４． 連続プロセスである、項１～３３のいずれか１項に記載の方法。
３５． ポリマーは、少なくとも０．１モル％の環状オレフィンを含む、項１～３４のいずれか１項に記載の方法。
３６． ポリマーは、少なくとも１モル％の環状オレフィンを含む、項１～３４のいずれか１項に記載の方法。
３７． ポリマーは、少なくとも１０モル％の環状オレフィンを含む、項１～３４のいずれか１項に記載の方法。
３８． ポリマーは、少なくとも１モル％の環状オレフィンおよび少なくとも２０モル％のエチレンを含む、項１～３７のいずれか１項に記載の方法。
３９． ポリマーは、少なくとも１モル％の環状オレフィンおよび少なくとも２０モル％のプロピレンを含む、項１～３７のいずれか１項に記載の方法。
４０． 置換または非置換シクロペンテンおよび置換または非置換２－ノルボルネンから選択される１つまたは複数の環状オレフィンモノマーを含む、項１～４０のいずれか１項に記載の方法により製造されるポリマー。
４１． 置換または非置換シクロペンテンから選択される１つまたは複数の環状モノマーを含む、項１～４０のいずれか１項に記載の方法により製造されるポリマー。
４２． 置換または非置換の２－ノルボルネンから選択される１つまたは複数の環状モノマーを含む、項１～３９のいずれか１項に記載の方法により製造されるポリマー。
４３． ポリマーは、置換または非置換シクロペンテンのホモポリマーである、項１～３３のいずれか１項に記載の方法。
４４． ポリマーはシクロペンテンのホモポリマーである、項４３に記載の方法。
４５． ポリマーは、
ａ．５，０００ｇ／モル超、あるいは１０，０００ｇ／モル超、あるいは１００，０００ｇ／モル超、あるいは１５０，０００ｇ／モル超のＭｎ；
ｂ．１０，０００ｇ／モル超、あるいは２０，０００ｇ／モル超、あるいは２００，０００ｇ／モル超、あるいは３００，０００ｇ／モル超のＭｗ；
ｃ．約１～１０、あるいは約１．５～５．０、あるいは約１．８～３．０、あるいは約２．０～４．０のＭｗ／Ｍｎ；
ｄ．０．１モル％以上、上限は５０モル％以下、あるいは４５モル％以下のシクロペンテン含有量；
ｅ．ポリマーに組み込まれた全シクロペンテン単位の約９０％以上でシクロペンテン１，２結合
を有する、エチレンシクロペンテンコポリマーである、項１～４０のいずれか１項に記載の方法。
４６． ポリマーは、
ａ．５０，０００ｇ／モル超、あるいは１００，０００ｇ／モル超、あるいは１５０，０００ｇ／モル超、あるいは２００，０００ｇ／モル超のＭｎ；
ｂ．１００，０００ｇ／モル超、あるいは２００，０００ｇ／モル超、あるいは３００，０００ｇ／モル超、あるいは４００，０００ｇ／モル超のＭｗ；
ｃ．約１．２～５．０、あるいは約１．５～４．０、あるいは約２．０～３．０のＭｗ／Ｍｎ；
ｄ．２０モル％以上、上限が８０モル％以下のノルボルネン含有量；
ｅ．１０～８０％の独立、１０～８０％の交互、１～５０％のブロックであるノルボルネン単位を有し、独立、交互、およびブロックの合計が１００％に等しい
エチレンノルボルネンコポリマーである、項１～４０のいずれか１項に記載の方法。
４７． ポリマーは、
ａ．３，０００ｇ／モル超、あるいは５，０００ｇ／モル超、あるいは１０，０００ｇ／モル超のＭｎ；
ｂ．６，０００ｇ／モル超、あるいは１０，０００ｇ／モル超、あるいは２０，０００ｇ／モル超のＭｗ；
ｃ．約１～１０、あるいは約１．５～５．０、あるいは約１．８～３．０、あるいは約２．０～４．０のＭｗ／Ｍｎ；
ｄ．０．１モル％以上、上限は５０モル％以下、あるいは４５モル％以下のシクロペンテン含有量；
ｅ．ポリマーに組み込まれた全シクロペンテン単位の約９０％以上でシクロペンテン１，２結合
を有する、プロピレンシクロペンテンコポリマーである、項１～４０のいずれか１項に記載の方法。
４８． ポリマーは、
ａ．３，０００ｇ／モル超、あるいは５，０００ｇ／モル超、あるいは１０，０００ｇ／モル超のＭｎ；
ｂ．６，０００ｇ／モル超、あるいは１０，０００ｇ／モル超、あるいは２０，０００ｇ／モル超のＭｗ；
ｃ．約１．２～５．０、あるいは約１．５～４．０、あるいは約２．０～３．０のＭｗ／Ｍｎ；
ｄ．１モル％以上、上限が５０モル％以下のノルボルネン含有量
を有する、プロピレンノルボルネンコポリマーである、項１～４０のいずれか１項に記載の方法。 The present invention relates to the following:
1. A cyclic olefin monomer and an optional comonomer selected from a _C2 - _C20 alpha olefin are reacted with an activator and a copolymer having the formula (I):

[Wherein:
M is a Group 3, 4, 5, or 6 transition metal or lanthanide;
E and E' are each independently O, S, or NR ⁹ , where R ⁹ is independently hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl, or a heteroatom-containing group;
Q is an atom of Group 14, 15, or 16 that forms a coordinate bond with the metal M;
A ¹ QA ^1′ is a portion of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms connecting A ² and A ^2′ by a three atom bridge, where Q is the central atom of the three atom bridge, A ¹ and A ^1′ are independently C, N, or C(R ²² ), and R ²² is selected from hydrogen, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ substituted hydrocarbyl;

is a divalent group containing 2 to 40 non-hydrogen atoms that connects ^A1 and the E-linked aryl group through a two atom bridge;

is a divalent group containing 2 to 40 non-hydrogen atoms that connects the A ^1′ and E′ linked aryl groups through a two atom bridge;
L is a Lewis base;
X is an anionic ligand;
n is 1, 2 or 3;
m is 0, 1, or 2;
n+m is 4 or less;
R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^2' , R ^3' , and R ^4' are each independently hydrogen, a C ₁ -C ₄₀ hydrocarbyl, a C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group;
one or more of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^1′ and R ^2′ , R ^2′ and R ^3′ , R ^3′ and R ^4′ may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, where substitutions on the rings may be joined to form additional rings;
Any two L groups may be combined to form a bidentate Lewis base;
The X group may be attached to the L group to form a monoanionic bidentate group;
Any two X groups may be combined to form a dianionic ligand.
A process for polymerization comprising contacting a catalyst compound represented by the formula:
2. The catalyst compound has the formula (II):

[Wherein:
M is a Group 3, 4, 5, or 6 transition metal or lanthanide;
E and E' are each independently O, S, or NR ⁹ , where R ⁹ is independently hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl, or a heteroatom-containing group;
Each L is independently a Lewis base;
n is 1, 2 or 3;
m is 0, 1, or 2;
n+m is 4 or less;
R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^2' , R ^3' , and R ^4' are each independently hydrogen, a C ₁ -C ₄₀ hydrocarbyl, a C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group;
one or more of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^1′ and R ^2′ , R ^2′ and R ^3′ , R ^3′ and R ^4′ may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, where substitutions on the rings may be joined to form additional rings;
Any two L groups may be combined to form a bidentate Lewis base;
The X group may be attached to the L group to form a monoanionic bidentate group;
Any two X groups may be combined to form a dianionic ligand;
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^5' , R ^6' , R ^7' , R ^8' , R ¹⁰ , R ¹¹ , and R ¹² are each independently hydrogen, a C ₁ -C ₄₀ hydrocarbyl, a C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group;
One or more ^{of R5} and ^R6 , ^R6 and ^R7 , ^R7 and ^R8 , R5 ^' and R6 ^' , R6 ^' and ^R7' , R7 ^' and R8 ^' , ^R10 and ^R11 , or ^R11 and ^R12 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, where substitutions on the rings may be joined to form additional rings.
The method according to claim 1, wherein the compound is represented by the formula:
3. The method according to item 1 or 2, wherein M is Hf, Zr or Ti.
4.
4. The method according to item 1, 2 or 3, wherein E and E' are each O.
5. The method of paragraph 1, 2, 3, or 4, wherein R ¹ and R ^1' are each independently a C ₄ -C ₄₀ tertiary hydrocarbyl group.
6. The method of paragraph 1, 2, 3, or 4, wherein R ¹ and R ^1' are each independently a C ₄ to _{C 40} cyclic tertiary hydrocarbyl group.
7. The method of paragraph 1, 2, 3, or 4, wherein R ¹ and R ^1' are each independently a C ₄ -C ₄₀ polycyclic tertiary hydrocarbyl group.
8. The method of any one of paragraphs 1 to 7, wherein each X is independently a substituted or unsubstituted hydrocarbyl radical having 1 to 20 carbon atoms, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halide, and combinations thereof (two Xs may form part of a fused ring or ring system).
9. The method of any one of paragraphs 1 to 8, wherein each L is independently an ether, a thioether, an amine, a phosphine, an ethyl ether, tetrahydrofuran, dimethylsulfide, triethylamine, pyridine, an alkene, an alkyne, an allene, and a carbene, and combinations thereof (optionally, two or more L may form part of a fused ring or ring system).
10. The method of claim 1, wherein M is Zr or Hf, Q is nitrogen, A ¹ and A ^1' are both carbon, E and E ^' are both oxygen, and R ¹ and R ^1' are both C ₄ -C ₂₀ cyclic tertiary alkyl.
11. The method of claim 1, wherein M is Zr or Hf, Q is nitrogen, A ¹ and A ^1' are both carbon, E and E ^' are both oxygen, and R ¹ and R ^1' are both adamantan-1-yl or substituted adamantan-1-yl.
12. The method of claim 1, wherein M is Zr or Hf, Q is nitrogen, A ¹ and A ^1′ are both carbon, E and E ^′ are both oxygen, X is methyl or chloro, and n is 2.
13. The method of claim 1, wherein Q is nitrogen, A ¹ and A ^1' are both carbon, R ¹ and R ^1' are both hydrogen, and E and E ^' are both NR ⁹ , where R ⁹ is selected from a C ₁ -C ₄₀ hydrocarbyl, a C ₁ -C ₄₀ substituted hydrocarbyl, or a heteroatom-containing group.
14. The method of claim 1, wherein Q is carbon, A ¹ and A ^1' are both nitrogen, and E and E ^' are both oxygen.
15. The method of claim 1, wherein Q is carbon, A ¹ is nitrogen, A ^1' is C(R ²² ), E and E ^' are both oxygen, and R ²² is selected from hydrogen, C ₁ -C ₂₀ hydrocarbyl, or C ₁ -C ₂₀ substituted hydrocarbyl.
16. Heterocyclic Lewis bases are represented by the formula:

wherein each R ²³ is independently selected from hydrogen, C ₁ -C ₂₀ alkyl, and C ₁ -C ₂₀ substituted alkyl.
Item 3. The method according to item 1, wherein the compound is selected from the group represented by:
17. The method of claim 2, wherein M is Zr or Hf, E and E ^' are both oxygen, and ^R1 and R1 ^' are both _C4 - _C20 cyclic tertiary alkyl.
18. The method of claim 2, wherein M is Zr or Hf, E and E ^' are both oxygen, and ^R1 and R1 ^' are both adamantan-1-yl or substituted adamantan-1-yl.
19. The method of claim 2, wherein M is Zr or Hf, E and E ^' are both oxygen, and each of R ¹ , R ¹ , R ³ and R ^3' is adamantan-1-yl or substituted adamantan-1-yl.
20. The method of claim 2, wherein M is Zr or Hf, E and E ^' are both oxygen, ^R1 and ^R1' are both _C4 - _C20 cyclic tertiary alkyl, and ^R7 and R7 ^' are both _C1 - _C20 alkyl.
21. The method of claim 2, wherein M is Zr or Hf, E and E ^' are both O, ^R1 and R1 ^' are both _C4 - _C20 cyclic tertiary alkyl, and ^R7 and R7 ^' are both _C1 - _C20 alkyl.
22. The method of claim 2, wherein M is Zr or Hf, E and E ^' are both O, ^R1 and R1 ^' are both _C4 - _C20 cyclic tertiary alkyl, and ^R7 and R7 ^' are both _C1 - _C3 alkyl.
23. The catalyst compound has the following formula:

Item 3. The method of claim 1, wherein the aryl group is one or more of the groups represented by
24. The catalyst compound has the following formula:

Item 3. The method of claim 1, wherein the aryl group is one or more of the groups represented by
25. The method of any one of paragraphs 1 to 24, wherein the activator comprises an alumoxane or a non-coordinating anion.
26. The method of any one of paragraphs 1 to 24, wherein the activator is soluble in a non-aromatic hydrocarbon solvent.
27. The method of any one of paragraphs 1 to 24, wherein the catalyst system does not include an aromatic solvent.
28. The activator has the formula:

where Z is (LH) or a reducible Lewis acid, L is a neutral Lewis base; H is hydrogen; (LH) ⁺ is a Bronsted acid; A ^d - is a non-coordinating anion having a charge d-; and d is an integer from 1 to 3.
Item 28. The method according to any one of items 1 to 27, wherein the compound is represented by the formula:
29. The activator has the formula:

[Wherein:
E is nitrogen or phosphorus;
d is 1, 2, or 3; k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6; n-k=d;
R ^1' , R ^2' , and R ^3' are independently C ₁ -C ₅₀ hydrocarbyl groups optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups;
wherein R ^1' , R ^2' , and R ^3' collectively contain 15 or more carbon atoms;
Mt is an element selected from Group 13 of the Periodic Table of the Elements;
Each Q is independently a hydride, a bridged or unbridged dialkylamide, a halide, an alkoxide, an aryloxide, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, or a halo-substituted hydrocarbyl group.
Item 28. The method according to any one of items 1 to 27, wherein the compound is represented by the formula:
30. The activator has the formula:

wherein A ^d − is a non-coordinating anion having a charge d−; d is an integer from 1 to 3; and (Z) _d ⁺ is

]
Item 28. The method according to any one of items 1 to 27, wherein the compound is represented by the formula:
31. The activator is:
N-methyl-4-nonadecyl-N-octadecylbenzeneaminium tetrakis(pentafluorophenyl)borate,
N-methyl-4-nonadecyl-N-octadecylbenzeneaminium tetrakis(perfluoronaphthalen-2-yl)borate,
dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate,
dioctadecylmethylammonium tetrakis(perfluoronaphthalen-2-yl)borate,
N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,
triphenylcarbenium tetrakis(pentafluorophenyl)borate,
trimethylammonium tetrakis(perfluoronaphthalen-2-yl)borate,
triethylammonium tetrakis(perfluoronaphthalen-2-yl)borate,
tripropylammonium tetrakis(perfluoronaphthalen-2-yl)borate,
tri(n-butyl)ammonium tetrakis(perfluoronaphthalen-2-yl)borate,
tri(t-butyl)ammonium tetrakis(perfluoronaphthalen-2-yl)borate,
N,N-dimethylanilinium tetrakis(perfluoronaphthalen-2-yl)borate,
N,N-diethylanilinium tetrakis(perfluoronaphthalen-2-yl)borate,
N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthalen-2-yl)borate,
tropylium tetrakis(perfluoronaphthalen-2-yl)borate,
triphenylcarbenium tetrakis(perfluoronaphthalen-2-yl)borate,
triphenylphosphonium tetrakis(perfluoronaphthalen-2-yl)borate,
triethylsilylium tetrakis(perfluoronaphthalen-2-yl)borate,
benzene(diazonium)tetrakis(perfluoronaphthalen-2-yl)borate,
trimethylammonium tetrakis(perfluorobiphenyl)borate,
triethylammonium tetrakis(perfluorobiphenyl)borate,
tripropylammonium tetrakis(perfluorobiphenyl)borate,
tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate,
tri(t-butyl)ammonium tetrakis(perfluorobiphenyl)borate,
N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,
N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate,
N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,
tropylium tetrakis(perfluorobiphenyl)borate,
triphenylcarbenium tetrakis(perfluorobiphenyl)borate,
triphenylphosphonium tetrakis(perfluorobiphenyl)borate,
triethylsilylium tetrakis(perfluorobiphenyl)borate,
benzene(diazonium)tetrakis(perfluorobiphenyl)borate,
[4- _t - _butyl - _PhNMe2H ][( _C6F3 ( _C6F5 ) ₂ ) _4B ],
trimethylammonium tetraphenylborate,
triethylammonium tetraphenylborate,
tripropylammonium tetraphenylborate,
tri(n-butyl)ammonium tetraphenylborate,
Tri(t-butyl)ammonium tetraphenylborate,
N,N-dimethylanilinium tetraphenylborate,
N,N-diethylanilinium tetraphenylborate,
N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,
tropylium tetraphenylborate,
triphenylcarbenium tetraphenylborate,
triphenylphosphonium tetraphenylborate,
Triethylsilylium tetraphenylborate,
Benzene(diazonium)tetraphenylborate,
trimethylammonium tetrakis(pentafluorophenyl)borate,
triethylammonium tetrakis(pentafluorophenyl)borate,
tripropylammonium tetrakis(pentafluorophenyl)borate,
tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,
tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,
N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,
N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,
N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,
tropylium tetrakis(pentafluorophenyl)borate,
triphenylcarbenium tetrakis(pentafluorophenyl)borate,
triphenylphosphonium tetrakis(pentafluorophenyl)borate,
triethylsilylium tetrakis(pentafluorophenyl)borate,
benzene(diazonium)tetrakis(pentafluorophenyl)borate,
trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,
dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
tropylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,
trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
tri(t-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
tropylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,
dicyclohexylammonium tetrakis(pentafluorophenyl)borate,
tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,
tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,
triphenylcarbenium tetrakis(perfluorophenyl)borate,
1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium,
tetrakis(pentafluorophenyl)borate,
4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, and triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate)
28. The method according to any one of the preceding claims, wherein the method is one or more of:
32. The method according to any one of items 1 to 31, which is a solution method.
33. The method of any one of paragraphs 1 to 32, carried out at a temperature of about 80° C. to about 300° C., a pressure in the range of about 0.35 MPa to about 10 MPa, and a residence time of 300 minutes or less.
34. The method of any one of paragraphs 1 to 33, which is a continuous process.
35. The method of any one of paragraphs 1 to 34, wherein the polymer comprises at least 0.1 mol % of a cyclic olefin.
36. The method of any one of paragraphs 1 to 34, wherein the polymer comprises at least 1 mol % of a cyclic olefin.
37. The method of any one of paragraphs 1 to 34, wherein the polymer comprises at least 10 mole % of a cyclic olefin.
38. The method of any one of paragraphs 1 to 37, wherein the polymer comprises at least 1 mol % cyclic olefin and at least 20 mol % ethylene.
39. The method of any one of paragraphs 1 to 37, wherein the polymer comprises at least 1 mol % cyclic olefin and at least 20 mol % propylene.
40. A polymer produced by the method of any one of paragraphs 1 to 40, comprising one or more cyclic olefin monomers selected from substituted or unsubstituted cyclopentene and substituted or unsubstituted 2-norbornene.
41. A polymer produced by the method of any one of paragraphs 1 to 40, comprising one or more cyclic monomers selected from substituted or unsubstituted cyclopentene.
42. A polymer produced by the method of any one of paragraphs 1 to 39, comprising one or more cyclic monomers selected from substituted or unsubstituted 2-norbornene.
43. The method of any one of paragraphs 1 to 33, wherein the polymer is a homopolymer of substituted or unsubstituted cyclopentene.
44. The method of claim 43, wherein the polymer is a homopolymer of cyclopentene.
45. The polymer is
a. Mn greater than 5,000 g/mol, alternatively greater than 10,000 g/mol, alternatively greater than 100,000 g/mol, alternatively greater than 150,000 g/mol;
b. Mw greater than 10,000 g/mol, alternatively greater than 20,000 g/mol, alternatively greater than 200,000 g/mol, alternatively greater than 300,000 g/mol;
c. Mw/Mn from about 1 to 10, alternatively from about 1.5 to 5.0, alternatively from about 1.8 to 3.0, alternatively from about 2.0 to 4.0;
d. a cyclopentene content of 0.1 mol% or more, up to 50 mol% or less, alternatively 45 mol% or less;
(e) The method of any one of paragraphs 1 to 40, wherein the copolymer is an ethylene cyclopentene copolymer having cyclopentene 1,2 bonds at about 90% or more of the total cyclopentene units incorporated in the polymer.
46. The polymer is
a. Mn greater than 50,000 g/mol, alternatively greater than 100,000 g/mol, alternatively greater than 150,000 g/mol, alternatively greater than 200,000 g/mol;
b. Mw greater than 100,000 g/mol, alternatively greater than 200,000 g/mol, alternatively greater than 300,000 g/mol, alternatively greater than 400,000 g/mol;
c. Mw/Mn from about 1.2 to 5.0, alternatively from about 1.5 to 4.0, alternatively from about 2.0 to 3.0;
d. a norbornene content of 20 mol% or more and 80 mol% or less;
e. The method of any one of paragraphs 1 to 40, wherein the ethylene norbornene copolymer has norbornene units which are 10-80% independent, 10-80% alternating, and 1-50% blocked, the sum of independent, alternating, and blocked equaling 100%.
47. The polymer is
a. Mn greater than 3,000 g/mol, alternatively greater than 5,000 g/mol, alternatively greater than 10,000 g/mol;
b. Mw greater than 6,000 g/mol, alternatively greater than 10,000 g/mol, alternatively greater than 20,000 g/mol;
c. Mw/Mn from about 1 to 10, alternatively from about 1.5 to 5.0, alternatively from about 1.8 to 3.0, alternatively from about 2.0 to 4.0;
d. a cyclopentene content of 0.1 mol% or more, up to 50 mol% or less, alternatively 45 mol% or less;
e) The method of any one of paragraphs 1 to 40, wherein the copolymer is a propylene cyclopentene copolymer, having cyclopentene 1,2 bonds at about 90% or more of the total cyclopentene units incorporated in the polymer.
48. The polymer is
a. Mn greater than 3,000 g/mol, alternatively greater than 5,000 g/mol, alternatively greater than 10,000 g/mol;
b. Mw greater than 6,000 g/mol, alternatively greater than 10,000 g/mol, alternatively greater than 20,000 g/mol;
c. Mw/Mn from about 1.2 to 5.0, alternatively from about 1.5 to 4.0, alternatively from about 2.0 to 3.0;
d. The method according to any one of items 1 to 40, wherein the copolymer is a propylene norbornene copolymer having a norbornene content of 1 mol % or more and an upper limit of 50 mol % or less.

Test methods for large scale polymerization Molecular weight and composition distribution (GPC-IR):
The distribution and moments of molecular weight (e.g., Mn, Mw, Mz) and comonomer distribution ( _C2 , _C3 , _C6 , etc.) are measured by high temperature gel permeation chromatography (PolymerChar GPC-IR) equipped with a multi-channel band filter-based infrared detector ensemble IR5, where a broadband channel is used to measure the polymer concentration and two narrowband channels to characterize the composition. Three Agilent PLgel 10 μm Mixed-B LS columns are used to separate the polymers. Aldrich reagent grade 1,2,4-trichlorobenzene (TCB) with 300 ppm of antioxidant butylated hydroxytoluene (BHT) is used as the mobile phase. The TCB mixture is filtered through a 0.1 micrometer Teflon filter and degassed with an online degasser before being loaded into the GPC instrument. The nominal flow rate is 1.0 mL/min and the nominal injection volume is 200 microliters. The entire system including the transfer line, column and detector is placed in an oven maintained at 145°C. A predetermined amount of polymer sample is weighed and sealed in a standard vial with 10 microliters of flow marker (heptane) added. After loading the vial into the autosampler, the polymer is dissolved automatically in the instrument by adding 8 mL of TCB solvent. The polymer is dissolved at 160°C with continuous shaking for about 1 hour for most PE samples and 2 hours for PP samples. The TCB density used to calculate the concentration is 1.463 g/ml at room temperature and 1.284 g/ml at 145°C. The concentration of the sample solution is 0.2-2.0 mg/ml, with lower concentrations used for high molecular weight samples.

The concentration c at each point in the chromatogram is calculated from the baseline-subtracted IR5 broadband signal I using the following formula:
c = αI
where α is the mass constant determined for the PE standard NBS 1475. Mass recovery is calculated from the ratio of the integrated area of the concentrated chromatography over the elution volume to the injected mass, which is equal to the given concentration multiplied by the injection loop volume.

式中、ＫとαはＭａｒｋ－Ｈｏｕｗｉｎｋ方程式の係数である。下付き「Ｘ」が付いた変数はテストサンプルを表し、下付き「ＰＳ」が付いた変数はポリスチレンを表す。この方法では、α_ＰＳ＝０．６７およびＫ_ＰＳ＝０．０００１７５、及びα_ＸおよびＫ_Ｘは、標準的な較正手順を使用して、線状エチレン／プロピレンコポリマーおよび線状エチレン－プロピレン－ジエンターポリマーの組成に基づいて決定される。コモノマー組成は、一連のＰＥおよびＰＰホモ／コポリマー標準で較正されたＣＨ_２およびＣＨ_３チャネルに対応するＩＲ検出器強度の比率によって決定される。 Molecular weights are determined by combining a column calibration performed with a series of monodisperse polystyrene (PS) standards and a universal calibration relationship. Molecular weights are calculated at each elution volume using the following formula:

where K and α are coefficients in the Mark-Houwink equation. Variables with the subscript "X" represent the test sample and variables with the subscript "PS" represent polystyrene. In this method, α _PS =0.67 and K _PS =0.000175, and α _X and K _X are determined based on the composition of linear ethylene/propylene copolymers and linear ethylene-propylene-diene terpolymers using standard calibration procedures. The comonomer composition is determined by the ratio of the IR detector intensities corresponding to the _CH2 and _CH3 channels calibrated with a series of PE and PP homo/copolymer standards.

The LS detector is an 18-sided Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model of static light scattering (Light Scattering from Polymer Solutions; Huglin, M. B., Ed.; Academic Press, 1972.).

式中、δＲ（θ）は、散乱角で測定された過剰レイリー散乱強度θであり、ｃはＩＲ５解析から決定されたポリマー濃度であり、Ａ_２は２番目のビリアル係数であり、Ｐ（θ）は単分散ランダムコイルのフォームファクターである。Ｋ_ｏはシステムの光学定数である。

式中、Ｎ_Ａはアボガドロ数であり、（ｄｎ／ｄｃ）は系の屈折率の増分である。１４５℃およびλ＝６６５ｎｍでのＴＣＢの屈折率ｎ＝１．５００である。ポリエチレンホモポリマー、エチレン－ヘキセンコポリマー、エチレン－オクテンコポリマーの分析では、ｄｎ／ｄｃ＝０．１０４８ｍｌ／ｍｇ、Ａ_２＝０．００１５であり；エチレン－ブテン共重合体の分析では、ｄｎ／ｄｃ＝０．１０４８^＊（１－０．００１２６^＊ｗ２）ｍｌ／ｍｇ、Ａ_２＝０．００１５（ｗ２はブテンコモノマーの重量パーセント）である。

where δR(θ) is the excess Rayleigh scattering intensity measured at the scattering angle θ, c is the polymer concentration determined from IR5 analysis, _A2 is the second virial coefficient, P(θ) is the form factor of a monodisperse random coil, _{and K0} are the optical constants of the system.

where N _A is Avogadro's number and (dn/dc) is the increment in refractive index of the system. The refractive index of TCB at 145° C. and λ=665 nm is n=1.500. For the analysis of polyethylene homopolymer, ethylene-hexene copolymer, and ethylene-octene copolymer, dn/dc=0.1048 ml/mg, A ₂ =0.0015; for the analysis of ethylene-butene copolymer, dn/dc=0.1048 ^* (1-0.00126 ^* w2) ml/mg, A ₂ =0.0015 (w2 is the weight percent of butene comonomer).

式中、α_ｐｓは０．６７であり、Ｋ_ＰＳは０．０００１７５である。 A high temperature Agilent (or Viscotek Corporation) with four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers is used to determine the viscosity. One transducer measures the pressure drop across the detector and the other is placed between the two sides of the bridge to measure the differential pressure. The specific viscosity, η _s , of the solution passing through the viscometer is calculated from their outputs. The intrinsic viscosity [η] at each point in the chromatogram is calculated from the equation [η] = η _S /c, where c is the concentration, determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as follows:

where α _ps is 0.67 and K _ps is 0.000175.

式中、合計は積分限界の間のクロマトグラフィースライスｉを超える。 The branching index ( _g'vis ) is calculated using the output of the GPC-IR5-LS-VIS method as follows: The average intrinsic viscosity [η]avg of the sample is calculated as follows: g'vis = g(vis)/ηavg.

where the sum is over the chromatographic slices i between the integration limits.

式中、ＭｖはＬＳ分析によって決定された分子量に基づく粘度平均分子量であり、Ｋおよびαは参照線状ポリマーの値であり、本開示の目的に関して、線状エチレンについてα＝０．６９５およびＫ＝０．０００５７９であり、線状プロピレンポリマーについてα＝０．７０５およびＫ＝０．０００２２８８、線状ブテンポリマーについてα＝０．６９５およびＫ＝０．０００１８１、エチレン－ブテンコポリマーについてαは０．６９５、Ｋは０．０００５７９＊（１－０．００８７＊ｗ２ｂ＋０．００００１８＊（ｗ２ｂ）＾２）、ここに、ｗ２ｂはブテンコモノマーのバルク重量パーセントであり、エチレン－ヘキセンコポリマーについてαは０．６９５、Ｋは０．０００５７９＊（１－０．００７５＊ｗ２ｂ）であり、ここに、ｗ２ｂはヘキセンコモノマーのバルク重量パーセントであり、エチレン－オクテンコポリマーについてαは０．６９５、Ｋは０．０００５７９＊（１－０．００７７＊ｗ２ｂ）であり、ここに、ｗ２ｂはオクテンコモノマーのバルク重量パーセントである。特記しない限り、濃度はｇ／ｃｍ^３で、分子量はｇ／ｍｏｌｅで、固有粘度（Ｍａｒｋ－Ｈｏｕｗｉｎｋ式中のＫ）はｄＬ／ｇで表される。ｗ２ｂ値の計算は、上記の通りである。 The branching index g' _vis is defined as follows:

where Mv is the viscosity average molecular weight based on molecular weight determined by LS analysis, K and α are values for reference linear polymers, which for purposes of this disclosure are: for linear ethylene, α=0.695 and K=0.000579; for linear propylene polymers, α=0.705 and K=0.0002288; for linear butene polymers, α=0.695 and K=0.000181; and for ethylene-butene copolymers, α is 0.695 and K is 0.000579*(1-0.0087*w2b+ α is 0.695, K is 0.000579*(1-0.0075*w2b) for ethylene-hexene copolymers, where w2b is the bulk weight percent of the hexene comonomer, and α is 0.695, K is 0.000579*(1-0.0077*w2b) for ethylene-octene copolymers, where w2b is the bulk weight percent of the octene comonomer. Unless otherwise stated, concentrations are in g/ ^cm3 , molecular weights are in g/mole, and intrinsic viscosity (K in the Mark-Houwink equation) is in dL/g. Calculation of w2b values is as described above.

Experimental and analytical details not described above, such as the detector calibration method, the composition dependence of the Mark-Houwink parameters, and the calculation method of the second virial coefficient, can be found in T. Sun, P. Brant, R. R. Chance, and W. W. Graessley (Macromolecules, 2001, v.34(19), pp. 6812-6820.

The peak melting point Tm (also referred to as melting point), peak crystallization temperature Tc (also referred to as crystallization temperature), glass transition temperature (Tg), heat of fusion (δHf or Hf), and percent crystallinity are determined using the following DSC procedure in accordance with ASTM D3418-03. Differential Scanning Calorimetry (DSC) data was obtained using a TA Instruments model DSC2500 machine. Samples weighing approximately 5-10 mg were sealed in aluminum hermetic sample pans. DSC data was recorded by first gradually heating the sample to 200°C at a rate of 10°C/min. The sample was held at 200°C for 2 minutes, then cooled to -90°C at a rate of 10°C/min, followed by isothermalization for 2 minutes and heating to 200°C at 10°C/min. Thermal events from both the first and second cycles were recorded. The area under the endothermic peak was measured and the heat of fusion and percent crystallinity were used to determine. Percent crystallinity is calculated using the formula [area under melting peak (joules/gram)/B (joules/gram)]*100, where B is the heat of fusion of a 100% crystalline homopolymer of the major monomeric component. These B values are taken from the Polymer Handbook, Fourth Edition, published by John Wiley and Sons, New York 1999, except that a value of 189 J/g (B) is used for the heat of fusion of 100% crystalline polypropylene and a value of 290 J/g is used for the heat of fusion of 100% crystalline polyethylene. Melting and crystallization temperatures reported herein were obtained during the second heating/cooling cycle unless otherwise noted.

For polymers that exhibit multiple endothermic and exothermic peaks, all peak crystallization temperatures and peak melting temperatures were reported. The heat of fusion for each endothermic peak was calculated separately. The percent crystallinity is calculated using the sum of the heats of fusion from all endothermic peaks. Some of the polymer blends produced exhibit secondary melting/cooling peaks that overlap with the main peak. These peaks are considered as a single melting/cooling peak. The highest point of these peaks is considered as the peak melting temperature/crystallization point. For amorphous polymers with relatively low crystallinity, the melting temperature is usually measured during the first heating cycle. Prior to DSC measurements, samples were aged (usually held at ambient temperature for 2 days) or annealed to maximize crystallinity.

The melt index (I ₂ ) was measured according to ASTM D1238 using a load of 2.16 kg at a temperature of 190° C. The melt index under high load conditions (I ₂₁ ) was measured according to ASTM D1238 using a load of 21.6 kg at a temperature of 190° C.

Density is determined in accordance with ASTM D1505 using a density gradient column on compression molded specimens that have been slowly cooled to room temperature (i.e., over 10 minutes) and aged for a sufficient time for the density to remain constant within +/- 0.001 g/ ^cm3 as described in ASTM D1505.

Experimental The catalysts used in the polymerizations reported herein were synthesized according to the procedures reported in US 2020-0255553, USSN 62/972953, USSN 62/972936, US 2020-0255555, US 2020-0254431, and US 2020-0255556.

Cat-Hf (complex 5), Cat-Zr (complex 6), and complex 66 were prepared as follows:

Starting material 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Aldrich)
2,6-Dibromopyridine (Aldrich), 2-bromoiodobenzene (Acros), 2.5 M ⁿ BuLi in hexane (Chemetall GmbH)), Pd(PPh ₃ ) ₄ (Aldrich), methoxymethyl chloride (Aldrich), NaH (60 wt % in mineral oil, Aldrich), THF (Merck), ethyl acetate (Merck), methanol (Merck), toluene (Merck)), hexane (Merck), dichloromethane (Merck), HfCl ₄ (<0.05% Zr, Strem), ZrCl ₄ (Strem), Cs ₂ CO ₃ (Merck), K ₂ CO ₃ (Merck), Na ₂ SO ₄ (Akzo Nobel), silica gel 60 (40-63 μm; Merck), and CDCl ₃ (Deutero GmbH) were used as received. Benzene-d ₆ (Deutero GmbH) and dichloromethane-d ₂ (Deutero GmbH) were dried with MS 4A before use. THF for organometallic syntheses was freshly distilled from sodium benzophenone ketyl. Toluene and hexane for organometallic syntheses were dried with MS 4A. 2-(adamantan-1-yl)-4-(tert-butyl)phenol was prepared from 4-tert-butylphenol (Merck) and adamantanol-1 (Aldrich) as described in Organic Letters, 2015, 17(9), 2242-2245.

５７．６ｇ（２０３ｍｍｏｌ）の２－（アダマンタン－１－イル）－４－（ｔｅｒｔ－ブチル）フェノールの４００ｍＬのクロロホルム溶液に、１０．４ｍＬ（２０３ｍｍｏｌ）の臭素の２００ｍＬのクロロホルム溶液を室温で３０分間かけて滴下した。得られた混合物を水４００ｍＬで希釈した。得られた混合物をジクロロメタン（３×１００ｍＬ）で抽出し、合わせた有機抽出物を５％ＮａＨＣＯ_３で洗浄し、Ｎａ_２ＳＯ_４で乾燥させ、次いで蒸発乾固した。収量７１．６ｇ（９７％）の白色固体。
¹H NMR (CDCl₃, 400 MHz): δ 7.32 (d, J = 2.3 Hz, 1 H), 7.19 (d, J = 2.3 Hz, 1 H), 5.65 (s, 1 H), 2.18 - 2.03 (m, 9 H), 1.78 (m, 6 H), 1.29 (s, 9 H). ¹³C NMR (CDCl₃, 100 MHz): δ 148.07, 143.75, 137.00, 126.04, 123.62, 112.11, 40.24, 37.67, 37.01, 34.46, 31.47, 29.03. 2-(adamantan-1-yl)-6-bromo-4-(tert-butyl)phenol

To a solution of 57.6 g (203 mmol) of 2-(adamantan-1-yl)-4-(tert-butyl)phenol in 400 mL of chloroform was added dropwise a solution of 10.4 mL (203 mmol) of bromine in 200 mL of chloroform at room temperature over 30 min. The resulting mixture was diluted with 400 mL of water. The resulting mixture was extracted with dichloromethane (3 x 100 mL) and the combined organic extracts were washed with 5% _NaHCO3 , dried _{over Na2SO4} and then evaporated to dryness. Yield 71.6 g (97%) of a white solid.
¹ H NMR (CDCl ₃ , 400 MHz): δ 7.32 (d, J = 2.3 Hz, 1 H), 7.19 (d, J = 2.3 Hz, 1 H), 5.65 (s, 1 H), 2.18 - 2.03 (m, 9 H), 1.78 (m, 6 H), 1.29 (s, 9 H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 148.07, 143.75, 137.00, 126.04, 123.62, 112.11, 40.24, 37.67, 37.01, 34.46, 31.47, 29.03.

７１．６ｇ（１９７ｍｍｏｌ）の２－（アダマンタン－１－イル）－６－ブロモ－４－（ｔｅｒｔ－ブチル）フェノールの１０００ｍＬのＴＨＦ溶液８．２８ｇ（２０７ｍｍｏｌ、ミネラル中の６０重量％、油中）の水素化ナトリウムを室温で少しずつ加えた。得られた懸濁液に、塩化メトキシメチル１６．５ｍＬ（２１７ｍｍｏｌ）を室温で１０分間かけて滴下した。得られた混合物を一晩攪拌した後、水１，０００ｍＬに注いだ。得られた混合物をジクロロメタン（３×３００ｍＬ）で抽出し、合わせた有機抽出物を５％ＮａＨＣＯ_３で洗浄し、Ｎａ_２ＳＯ_４で乾燥させ、次いで蒸発乾固させた。収量８０．３ｇ（～ｑｕａｎｔ）の白色固体。
¹H NMR (CDCl₃, 400 MHz): δ 7.39 (d, J = 2.4 Hz, 1 H), 7.27 (d, J = 2.4 Hz, 1 H), 5.23 (s, 2 H), 3.71 (s, 3 H), 2.20 - 2.04 (m, 9 H), 1.82 - 1.74 (m, 6 H), 1.29 (s, 9 H). ¹³C NMR (CDCl₃, 100 MHz): δ 150.88, 147.47, 144.42, 128.46, 123.72, 117.46, 99.53, 57.74, 41.31, 38.05, 36.85, 34.58, 31.30, 29.08. 1-(3-bromo-5-(tert-butyl)-2-(methoxymethoxy)phenyl)adamantane

A solution of 71.6 g (197 mmol) of 2-(adamantan-1-yl)-6-bromo-4-(tert-butyl)phenol in 1000 mL of THF and 8.28 g (207 mmol, 60% by weight in mineral, in oil) of sodium hydride was added portionwise at room temperature. To the resulting suspension, 16.5 mL (217 mmol) of methoxymethyl chloride was added dropwise over 10 min at room temperature. The resulting mixture was stirred overnight and then poured into 1,000 mL of water. The resulting mixture was extracted with dichloromethane (3×300 mL) and the combined organic extracts were washed with 5% NaHCO ₃ , dried over Na ₂ SO ₄ and then evaporated to dryness. Yield 80.3 g (~quant) of white solid.
¹ H NMR (CDCl ₃ , 400 MHz): δ 7.39 (d, J = 2.4 Hz, 1 H), 7.27 (d, J = 2.4 Hz, 1 H), 5.23 (s, 2 H), 3.71 (s, 3 H), 2.20 - 2.04 (m, 9 H), 1.82 - 1.74 (m, 6 H), 1.29 (s, 9 H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 150.88, 147.47, 144.42, 128.46, 123.72, 117.46, 99.53, 57.74, 41.31, 38.05, 36.85, 34.58, 31.30, 29.08.

２２．５ｇ（５５．０ミリモル）の１－（３－ブロモ－５－（ｔｅｒｔ－ブチル）－２－（メトキシメトキシ）フェニル）アダマンタンの３００ｍＬ乾燥ＴＨＦ溶液に２３．２ｍＬ（５７．９ミリモル、２．５Ｍ）の^ｎＢｕＬｉのヘキサン溶液を－８０℃で２０分間滴下した。反応混合物をこの温度で１時間撹拌し、続いて１４．５ｍＬ（７１．７ｍｍｏｌ）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを添加した。得られた懸濁液を室温で１時間攪拌した後、水３００ｍＬに注いだ。得られた混合物をジクロロメタン（３×３００ｍＬ）で抽出し、合わせた有機抽出物をＮａ_２ＳＯ_４で乾燥させ、次いで蒸発乾固させた。収量２５．０ｇ（～ｑｕａｎｔ）の無色の粘性油。
1H NMR (CDCl3, 400 MHz): δ 7.54 (d, J = 2.5 Hz, 1 H), 7.43 (d, J = 2.6 Hz, 1 H), 5.18 (s, 2 H), 3.60 (s, 3 H), 2.24 - 2.13 (m, 6 H), 2.09 (br. s., 3 H), 1.85 - 1.75 (m, 6 H), 1.37 (s, 12 H), 1.33 (s, 9 H). 13C NMR (CDCl3, 100 MHz): δ 159.64, 144.48, 140.55, 130.58, 127.47, 100.81, 83.48, 57.63, 41.24, 37.29, 37.05, 34.40, 31.50, 29.16, 24.79. (2-(3-adamantan-1-yl)-5-(tert-butyl)-2-(methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

A solution of 23.2 mL (57.9 mmol, 2.5 M) of ⁿ BuLi in hexane was added dropwise to a solution of 22.5 g (55.0 mmol) of 1-(3-bromo-5-(tert-butyl)-2-(methoxymethoxy)phenyl)adamantane in 300 mL of dry THF at −80° C. for 20 min. The reaction mixture was stirred at this temperature for 1 h, followed by the addition of 14.5 mL (71.7 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting suspension was stirred at room temperature for 1 h and then poured into 300 mL of water. The resulting mixture was extracted with dichloromethane (3×300 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. Yield 25.0 g (∼quant) of a colorless viscous oil.
1H NMR (CDCl3, 400 MHz): δ 7.54 (d, J = 2.5 Hz, 1 H), 7.43 (d, J = 2.6 Hz, 1 H), 5.18 (s, 2 H), 3.60 (s, 3 H), 2.24 - 2.13 (m, 6 H), 2.09 (br. 13C NMR (CDCl3, 100 MHz): δ 159.64, 144.48, 140.55, 130.58, 127.47, 100.81, 83.48, 57.63, 41.24, 37.29, 37.05, 34.40, 31.50, 29.16, 24.79.

（２－（３－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－２－（メトキシメトキシ）フェニル）－４，４，５，５－テトラメチル－２５．０ｇ（５５．０ｍｍｏｌ）の溶液に、２００ｍＬのジオキサン中の１，３，２－ジオキサボロラン１５．６ｇ（５５．０ミリモル）の２－ブロモヨードベンゼン、１９．０ｇ（１３７ミリモル）の炭酸カリウム、および１００ｍＬの水を続いて添加した。得られた混合物をアルゴンで１０分間パージし、続いて３．２０ｇ（２．７５ミリモル）のＰｄ（ＰＰｈ_３）_４を添加した。得られた混合物を１００℃で１２時間攪拌した後、室温まで冷却し、水１００ｍＬで希釈した。得られた混合物をジクロロメタン（３×１００ｍＬ）で抽出し、合わせた有機抽出物をＮａ_２ＳＯ_４で乾燥させ、次いで蒸発乾固させた。残留物をシリカゲル６０（４０～６３μｍ、溶離剤：ヘキサン－ジクロロメタン＝１０：１、体積）でのフラッシュクロマトグラフィーにより精製した。収量２３．５ｇ（８８％）の白色固体。
1H NMR (CDCl3, 400 MHz): δ 7.68 (dd, J = 1.0, 8.0 Hz, 1 H), 7.42 (dd, J = 1.7, 7.6 Hz, 1 H), 7.37 - 7.32 (m, 2 H), 7.20 (dt, J = 1.8, 7.7 Hz, 1 H), 7.08 (d, J = 2.5 Hz, 1 H), 4.53 (d, J = 4.6 Hz, 1 H), 4.40 (d, J = 4.6 Hz, 1 H), 3.20 (s, 3 H), 2.23 - 2.14 (m, 6 H), 2.10 (br. s., 3 H), 1.86 - 1.70 (m, 6 H), 1.33 (s, 9 H). 13C NMR (CDCl3, 100 MHz): δ 151.28, 145.09, 142.09, 141.47, 133.90, 132.93, 132.41, 128.55, 127.06, 126.81, 124.18, 123.87, 98.83, 57.07, 41.31, 37.55, 37.01, 34.60, 31.49, 29.17. 1-(2'-bromo-5-(tert-butyl)-2-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)adamantane

To a solution of 25.0 g (55.0 mmol) of (2-(3-adamantan-1-yl)-5-(tert-butyl)-2-(methoxymethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 15.6 g (55.0 mmol) of 2-bromoiodobenzene, 19.0 g (137 mmol) of potassium carbonate, and 100 mL of water were added successively in 200 mL of dioxane. The resulting mixture was purged with argon for 10 min, followed by the addition of 3.20 g (2.75 mmol) of Pd(PPh ₃ ) _4. The resulting mixture was stirred at 100° C. for 12 h, then cooled to room temperature and diluted with 100 mL of water. The resulting mixture was extracted with dichloromethane (3×100 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane=10:1, by volume). Yield 23.5 g (88%) of a white solid.
1H NMR (CDCl3, 400 MHz): δ 7.68 (dd, J = 1.0, 8.0 Hz, 1 H), 7.42 (dd, J = 1.7, 7.6 Hz, 1 H), 7.37 - 7.32 (m, 2 H), 7.20 (dt, J = 1.8, 7.7 Hz, 1 H), 7.08 (d, J = 2.5 Hz, 1 H), 4.53 (d, J = 4.6 Hz, 1 H), 4.40 (d, J = 4.6 Hz, 1 H), 3.20 (s, 3 H), 2.23 - 2.14 (m, 6 H), 2.10 (br. s., 3 H), 1.86 - 1.70 (m, 6 H), 1.33 (s, 9 H). 13C NMR (CDCl3, 100 MHz): δ 151.28, 145.09, 142.09, 141.47, 133.90, 132.93, 132.41, 128.55, 127.06, 126.81, 124.18, 123.87, 98.83, 57.07, 41.31, 37.55, 37.01, 34.60, 31.49, 29.17.

５００ｍＬ中の１－（２’－ブロモ－５－（ｔｅｒｔ－ブチル）－２－（メトキシメトキシ）－［１，１’－ビフェニル］－３－イル）アダマンタン３０．０ｇ（６２．１ｍｍｏｌ）の溶液に、ヘキサン中のｎＢｕＬｉ２５．６ｍＬ（６３．９ｍｍｏｌ、２．５Ｍ）の乾燥ＴＨＦを、－８０℃で２０分間滴下した。反応混合物をこの温度で１時間撹拌し、続いて１６．５ｍＬ（８０．７ミリモル）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを添加した。得られた懸濁液を室温で１時間攪拌した後、水３００ｍＬに注いだ。得られた混合物をジクロロメタン（３×３００ｍＬ）で抽出し、合わせた有機抽出物をＮａ_２ＳＯ_４で乾燥させ、次いで蒸発乾固させた。収量３２．９ｇ（～ｑｕａｎｔ．）の無色のガラス状の固体。
1H NMR (CDCl3, 400 MHz): δ 7.75 (d, J = 7.3 Hz, 1 H), 7.44 - 7.36 (m, 1 H), 7.36 - 7.30 (m, 2 H), 7.30 - 7.26 (m, 1 H), 6.96 (d, J = 2.4 Hz, 1 H), 4.53 (d, J = 4.7 Hz, 1 H), 4.37 (d, J = 4.7 Hz, 1 H), 3.22 (s, 3 H), 2.26 - 2.14 (m, 6 H), 2.09 (br. s., 3 H), 1.85 - 1.71 (m, 6 H), 1.30 (s, 9 H), 1.15 (s, 6 H), 1.10 (s, 6 H). 13C NMR (CDCl3, 100 MHz): δ 151.35, 146.48, 144.32, 141.26, 136.15, 134.38, 130.44, 129.78, 126.75, 126.04, 123.13, 98.60, 83.32, 57.08, 41.50, 37.51, 37.09, 34.49, 31.57, 29.26, 24.92, 24.21. 2-(3'-(adamantan-1-yl)-5'-(tert-butyl)-2'-(methoxymethoxy)-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

To a solution of 30.0 g (62.1 mmol) of 1-(2'-bromo-5-(tert-butyl)-2-(methoxymethoxy)-[1,1'-biphenyl]-3-yl)adamantane in 500 mL of dry THF was added dropwise at -80 °C for 20 min with 25.6 mL (63.9 mmol, 2.5 M) of nBuLi in hexane. The reaction mixture was stirred at this temperature for 1 h, followed by the addition of 16.5 mL (80.7 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting suspension was stirred at room temperature for 1 h and then poured into 300 mL of water. The resulting mixture was extracted with dichloromethane (3 x 300 mL) and the combined organic extracts were dried _{over Na2SO4} and then evaporated to dryness. Yield 32.9 g (.about.quant.) of a colorless glassy solid.
1H NMR (CDCl3, 400 MHz): δ 7.75 (d, J = 7.3 Hz, 1 H), 7.44 - 7.36 (m, 1 H), 7.36 - 7.30 (m, 2 H), 7.30 - 7.26 (m, 1 H), 6.96 (d, J = 2.4 Hz, 1 H), 4.53 (d, J = 4.7 Hz, 1 H), 4.37 (d, J = 4.7 Hz, 1 H), 3.22 (s, 3 H), 2.26 - 2.14 (m, 6 H), 2.09 (br. s., 3 H), 1.85 - 1.71 (m, 6 H), 1.30 (s, 9H), 1.15 (s, 6H), 1.10 (s, 6 H). 13C NMR (CDCl3, 100 MHz): δ 151.35, 146.48, 144.32, 141.26, 136.15, 134.38, 130.44, 129.78, 126.75, 126.04, 123.13, 98.60, 83.32, 57.08, 41.50, 37.51, 37.09, 34.49, 31.57, 29.26, 24.92, 24.21.

2-(3'-(アダマンタン-1-イル)-5－（ｔｅｒｔ－ブチル）－２’－（メトキシメトキシ）－［１，１’－ビフェニル］－２－イル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン３２．９ｇ（６２．０ｍｍｏｌ）の溶液に（１４０ｍＬのジオキサン中）、７．３５ｇ（３１．０ｍｍｏｌ）の２，６－ジブロモピリジン、５０．５ｇ（１５５ｍｍｏｌ）の炭酸セシウム、および続いて水７０ｍＬを添加した。得られた混合物をアルゴンで１０分間パージし、続いて３．５０ｇ（３．１０ミリモル）のＰｄ（ＰＰｈ_３）_４を添加した。この混合物を１００℃で１２時間攪拌し、次いで室温まで冷却し、５０ｍＬの水で希釈した。得られた混合物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ_２ＳＯ_４で乾燥させ、次いで蒸発乾固させた。得られた油に、３００ｍＬのＴＨＦ、３００ｍＬのメタノール、および２１ｍＬの１２ＮのＨＣｌを続けて添加した。反応混合物を６０℃で一晩撹拌し、次いで５００ｍＬの水に注いだ。得られた混合物をジクロロメタン（３×３５０ｍＬ）で抽出し、合わせた有機抽出物を５％ＮａＨＣＯ_３で洗浄し、Ｎａ_２ＳＯ_４で乾燥させ、次いで蒸発乾固した。残留物をシリカゲル６０（４０～６３μｍ、溶離剤：ヘキサン－酢酸エチル＝１０：１、体積）でのフラッシュクロマトグラフィーにより精製した。得られたガラス状の固体を７０ｍＬのｎ－ペンタンで摩砕し、得られた沈殿物を濾別し、２×２０ｍＬのｎ－ペンタンで洗浄し、真空乾燥した。収量２１．５ｇ（８７％）の２つの異性体の白色粉末としての混合物。
¹H NMR (CDCl₃, 400 MHz): δ 8.10 + 6.59 (2s, 2H), 7.53 - 7.38 (m, 10H), 7.09 + 7.08 (2d, J = 2.4 Hz, 2H), 7.04 + 6.97 (2d, J = 7.8 Hz, 2H), 6.95 + 6.54 (2d, J = 2.4 Hz), 2.03 - 1.79 (m, 18H), 1.74 - 1.59 (m, 12H), 1.16 + 1.01 (2s, 18H). ¹³C NMR (CDCl₃, 100 MHz, * で標識された少量の異性体シフト): δ 157.86, 157.72*, 150.01, 149.23*, 141.82*, 141.77, 139.65*, 139.42, 137.92, 137.43, 137.32*, 136.80, 136.67*, 136.29*, 131.98*, 131.72, 130.81, 130.37*, 129.80, 129.09*, 128.91, 128.81*, 127.82*, 127.67, 126.40, 125.65*, 122.99*, 122.78, 122.47, 122.07*, 40.48, 40.37*, 37.04, 36.89*, 34.19*, 34.01, 31.47, 29.12, 29.07*. (2',2'''-(pyridine-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol))

To a solution of 32.9 g (62.0 mmol) of 2-(3'-(adamantan-1-yl)-5-(tert-butyl)-2'-(methoxymethoxy)-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane in 140 mL of dioxane was added 7.35 g (31.0 mmol) of 2,6-dibromopyridine, 50.5 g (155 mmol) of cesium carbonate, followed by 70 mL of water. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 3.50 g (3.10 mmol) of Pd( _PPh3 ) ₄ . The mixture was stirred at 100°C for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The resulting mixture was extracted with dichloromethane (3×50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. To the resulting oil, 300 mL of THF, 300 mL of methanol, and 21 mL of 12N HCl were successively added. The reaction mixture was stirred at 60° C. overnight and then poured into 500 mL of water. The resulting mixture was extracted with dichloromethane (3×350 mL) and the combined organic extracts were washed with 5% NaHCO ₃ , dried over Na ₂ SO ₄ , and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, by volume). The resulting glassy solid was triturated with 70 mL of n-pentane and the resulting precipitate was filtered off, washed with 2×20 mL of n-pentane, and dried in vacuum. Yield 21.5 g (87%) of a mixture of two isomers as a white powder.
^1H NMR ( _CDCl3 , 400 MHz): δ 8.10 + 6.59 (2s, 2H), 7.53 - 7.38 (m, 10H), 7.09 + 7.08 (2d, J = 2.4 Hz, 2H), 7.04 + 6.97 (2d, J = 7.8 Hz, 2H), 6.95 + 6.54 (2d, J = 2.4 Hz), 2.03 - 1.79 (m, 18H), 1.74 - 1.59 (m, 12H), 1.16 + 1.01 (2s, 18H). ^13C NMR ( _CDCl3 , 100 MHz, minor isomer shifts labeled with *): δ 157.86, 157.72*, 150.01, 149.23*, 141.82*, 141.77, 139.65*, 139.42, 137.92, 137.43, 137.32*, 136.80, 136.67*, 136.29*, 131.98*, 131.72, 130.81, 130.37*, 129.80, 129.09*, 128.91, 128.81*, 127.82*, 127.67, 126.40, 125.65*, 122.99*, 122.78, 122.47, 122.07*, 40.48, 40.37*, 37.04, 36.89*, 34.19*, 34.01, 31.47, 29.12, 29.07*.

２５０ｍＬの乾燥トルエン中の３．２２ｇ（１０．０５ｍｍｏｌ）の四塩化ハフニウム（＜０．０５％Ｚｒ）の懸濁液に、ジエチルエーテル中の１４．６ｍＬ（４２．２ｍｍｏｌ、２．９Ｍ）のＭｅＭｇＢｒを注射器で０℃で一度に加えた。得られた懸濁液を１分間攪拌し、８．００ｇ（１０．０５ｍｍｏｌ）の（２’，２’’’－（ピリジン－２，６－ジイル）ビス（（３－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－［１，１’－ビフェニル］－２－オール））を１分間かけて少しずつ加えた。反応混合物を室温で３６時間攪拌し、次いで蒸発乾固した。得られた固体を熱トルエン２×１００ｍＬで抽出し、合わせた有機抽出物をセライト５０３の薄いパッドを通して濾過した。次に、濾液を蒸発乾固させた。残渣を５０ｍＬのｎ－ヘキサンで摩砕し、得られた沈殿物を濾別し（Ｇ３）、２０ｍＬのｎ－ヘキサン（２×２０ｍＬ）で洗浄し、次いで真空乾燥した。収量６．６６ｇ（６１％、ｎ－ヘキサンとの～１：１溶媒和物）の明るいベージュ色の固体。
C₅₉H₆₉HfNO₂×1.0(C₆H₁₄)として計算値: C, 71.70; H, 7.68; N, 1.29. 実測値: C 71.95; H, 7.83; N 1.18. ¹H NMR (C₆D₆, 400 MHz): δ 7.58 (d, J = 2.6 Hz, 2 H), 7.22 - 7.17 (m, 2 H), 7.14 - 7.08 (m, 4 H), 7.07 (d, J = 2.5 Hz, 2 H), 7.00 - 6.96 (m, 2 H), 6.48 - 6.33 (m, 3 H), 2.62 - 2.51 (m, 6H), 2.47 - 2.35 (m, 6H), 2.19 (br.s, 6H), 2.06 - 1.95 (m, 6H), 1.92 - 1.78 (m, 6H), 1.34 (s, 18 H), -0.12 (s, 6 H). ¹³C NMR (C₆D₆, 100 MHz): δ 159.74, 157.86, 143.93, 140.49, 139.57, 138.58, 133.87, 133.00, 132.61, 131.60, 131.44, 127.98, 125.71, 124.99, 124.73, 51.09, 41.95, 38.49, 37.86, 34.79, 32.35, 30.03. Dimethylhafnium(2',2''-(pyridine-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-oleate)) (Cat-Hf; Complex 5)

To a suspension of 3.22 g (10.05 mmol) of hafnium tetrachloride (<0.05% Zr) in 250 mL of dry toluene was added 14.6 mL (42.2 mmol, 2.9 M) of MeMgBr in diethyl ether in one portion via syringe at 0° C. The resulting suspension was stirred for 1 min and 8.00 g (10.05 mmol) of (2′,2′′-(pyridine-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1′-biphenyl]-2-ol)) was added in portions over 1 min. The reaction mixture was stirred at room temperature for 36 h and then evaporated to dryness. The resulting solid was extracted with 2×100 mL of hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 50 mL of n-hexane and the resulting precipitate was filtered off (G3), washed with 20 mL of n-hexane (2×20 mL) and then dried under vacuum. Yield 6.66 g (61%, ∼1:1 solvate with n-hexane) of a light beige solid.
Calculated as C ₅₉ H ₆₉ HfNO ₂ ×1.0(C ₆ H ₁₄ ): C, 71.70; H, 7.68; N, 1.29. Actual value: C 71.95; H, 7.83; N 1.18. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.58 (d, J = 2.6 Hz, 2 H), 7.22 - 7.17 (m, 2 H), 7.14 - 7.08 (m, 4 H), 7.07 (d, J = 2.5 Hz, 2 H), 7.00 - 6.96 (m, 2 H), 6.48 - 6.33 (m, 3 H), 2.62 - 2.51 (m, 6H), 2.47 - 2.35 (m, 6H), 2.19 (br.s, 6H), 2.06 - 1.95 (m, 6H), 1.92 - 1.78 (m, 6H), 1.34 (s, 18 H), -0.12 (s, 6 H). ¹³ C NMR (C ₆ D ₆ , 100 MHz): δ 159.74, 157.86, 143.93, 140.49, 139.57, 138.58, 133.87, 133.00, 132.61, 131.60, 131.44, 127.98, 125.71, 124.99, 124.73, 51.09, 41.95, 38.49, 37.86, 34.79, 32.35, 30.03.

３００ｍＬの乾燥トルエン中の２．９２ｇ（１２．５６ミリモル）の四塩化ジルコニウムの懸濁液に、ジエチルエーテル中の１８．２ｍＬ（５２．７ミリモル、２．９Ｍ）のＭｅＭｇＢｒを注射器を介して０℃で一度に加えた。得られた懸濁液に、１０．００ｇ（１２．５６ミリモル）の（２’，２’’’－（ピリジン－２，６－ジイル）ビス（（３－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－［１，１’－ビフェニル］－２－オール））をすぐに一度に添加した。反応混合物を室温で２時間撹拌し、次いで蒸発させてほぼ乾燥させた。得られた固体を熱トルエン２×１００ｍＬで抽出し、合わせた有機抽出物をセライト５０３の薄いパッドを通して濾過した。次に、濾液を蒸発乾固させた。残渣を５０ｍＬのｎ－ヘキサンで摩砕し、得られた沈殿物を濾別し（Ｇ３）、ｎ－ヘキサン（２×２０ｍＬ）で洗浄し、次いで真空乾燥した。収量８．９５ｇ（７４％、ｎ－ヘキサンとの～１：０．５溶媒和物）のベージュ色の固体。
C₅₉H₆₉ZrNO₂×0.5(C₆H₁₄)として計算値: C, 77.69; H, 7.99; N, 1.46. 実測値: C 77.90; H, 8.15; N 1.36. ¹H NMR (C₆D₆, 400 MHz): δ 7.56 (d, J = 2.6 Hz, 2 H), 7.20 - 7.17 (m, 2 H), 7.14 - 7.07 (m, 4 H), 7.07 (d, J = 2.5 Hz, 2 H), 6.98 - 6.94 (m, 2 H), 6.52 - 6.34 (m, 3 H), 2.65 - 2.51 (m, 6H), 2.49 - 2.36 (m, 6H), 2.19 (br.s., 6H), 2.07 - 1.93 (m, 6H), 1.92 - 1.78 (m, 6H), 1.34 (s, 18 H), 0.09 (s, 6 H). ¹³C NMR (C₆D₆, 100 MHz): δ 159.20, 158.22, 143.79, 140.60, 139.55, 138.05, 133.77, 133.38, 133.04, 131.49, 131.32, 127.94, 125.78, 124.65, 124.52, 42.87, 41.99, 38.58, 37.86, 34.82, 32.34, 30.04. Dimethylzirconium (2',2''-(pyridine-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-oleate)) (Cat-Zr; Complex 6)

To a suspension of 2.92 g (12.56 mmol) of zirconium tetrachloride in 300 mL of dry toluene was added 18.2 mL (52.7 mmol, 2.9 M) of MeMgBr in diethyl ether in one portion via syringe at 0° C. To the resulting suspension was added 10.00 g (12.56 mmol) of (2′,2′′-(pyridine-2,6-diyl)bis((3-adamantan-1-yl)-5-(tert-butyl)-[1,1′-biphenyl]-2-ol)) in one portion immediately. The reaction mixture was stirred at room temperature for 2 h and then evaporated to near dryness. The resulting solid was extracted with 2×100 mL of hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. The filtrate was then evaporated to dryness. The residue was triturated with 50 mL of n-hexane and the resulting precipitate was filtered off (G3), washed with n-hexane (2×20 mL) and then dried under vacuum. Yield 8.95 g (74%, ∼1:0.5 solvate with n-hexane) of a beige solid.
Calculated for _{C59H69ZrNO2 x 0.5 (C6H14 )} : C, 77.69; H, 7.99; N, 1.46. Found: C _77.90 ; H, 8.15; N, 1.36. ^1H NMR ( _{C6D6 ,} 400 MHz): δ 7.56 (d, J = 2.6 Hz, 2H), 7.20 - 7.17 (m, 2H), 7.14 - 7.07 (m, 4H), 7.07 (d, J = 2.5 Hz, 2H), 6.98 - 6.94 (m, 2H), 6.52 - 6.34 (m, 3H), 2.65 - 2.51 (m, 6H), 2.49 - 2.36 (m, 6H), 2.19 (br.s., 6H), 2.07 - 1.93 (m, 6H), 1.92 - 1.78 (m, 6H), 1.34 (s, 18 H), 0.09 (s, 6 H). ¹³ C NMR (C ₆ D ₆ , 100 MHz): δ 159.20, 158.22, 143.79, 140.60, 139.55, 138.05, 133.77, 133.38, 133.04, 131.49, 131.32, 127.94, 125.78, 124.65, 124.52, 42.87, 41.99, 38.58, 37.86, 34.82, 32.34, 30.04.

ヘキサン（１００ｍＬ）を１－（２－（メトキシメトキシ）－５－（２，４，４－トリメチルペンタン－２－イル）フェニル）アダマンタン（１２．１５ｇ、３１．５９ミリモル）に加えて、透明な淡黄色溶液を形成した。ＢｕＬｉ（１２．６９ｍＬ、３１．５９ミリモル）を滴下して、黄色の溶液を形成した。ＤＭＥ（３．２８４ｍＬ、３１．５９ｍｍｏｌ）を素早く加えた。一晩攪拌した後、フリット上に白色固体を集め、ヘキサン（３×１０ｍＬ）で洗浄した。固体を減圧下で乾燥させた。Ｈ ＮＭＲ分析は、０．８８当量のＤＭＥの存在を示した。さらに精製することなく使用した。収量：８．３６ｇ、５６．３％。 (3-(adamantan-1-yl)-2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)lithium

Hexanes (100 mL) was added to 1-(2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)adamantane (12.15 g, 31.59 mmol) to form a clear pale yellow solution. BuLi (12.69 mL, 31.59 mmol) was added dropwise to form a yellow solution. DME (3.284 mL, 31.59 mmol) was added quickly. After stirring overnight, a white solid was collected on a frit and washed with hexanes (3 × 10 mL). The solid was dried under reduced pressure. H NMR analysis indicated the presence of 0.88 equivalents of DME. Used without further purification. Yield: 8.36 g, 56.3%.

トルエン（１２０ｍＬ）を、（３－（アダマンタン－１－イル）－２－（メトキシメトキシ）－５－（２，４，４－トリメチルペンタン－２－イル）フェニル）リチウム（ｄｍｅ）_０．８８（８．３６ｇ、１７．７９ｍｍｏｌ）に加え、懸濁液を形成した。１－ブロモ－２－クロロベンゼン（３．７４７ｇ、１９．５７ｍｍｏｌ）のトルエン溶液（２５ｍＬ）を３．５時間かけて滴下した。一晩攪拌した後、濁った混合物を分液漏斗に移し、水（５×５０ｍＬ）、次いでブライン（２×１０ｍＬ）で抽出した。有機物をＭｇＳＯ_４で乾燥させ、濾過し、蒸発させて淡黄色の油を得た。Ｈ ＮＭＲは、粗生成物中のトルエンの０．５当量の存在を示した。さらに精製することなく使用した。収量：９．９２ｇ、９５．２％。 1-(2'-bromo-2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-3-yl)adamantane.

Toluene (120 mL) was added to (3-(adamantan-1-yl)-2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl)lithium (dme) _0.88 (8.36 g, 17.79 mmol) to form a suspension. A solution of 1-bromo-2-chlorobenzene (3.747 g, 19.57 mmol) in toluene (25 mL) was added dropwise over 3.5 h. After stirring overnight the cloudy mixture was transferred to a separatory funnel and extracted with water (5 x 50 mL) then brine (2 x 10 mL). The organics were dried over _MgSO4 , filtered and evaporated to give a pale yellow oil. H NMR indicated the presence of 0.5 equivalents of toluene in the crude product. Used without further purification. Yield: 9.92 g, 95.2%.

ヘキサン（２００ｍＬ）を１－（２’－ブロモ－２－（メトキシメトキシ）－５－（２，４，４－トリメチルペンタン－２－イル）－［１，１’－ビフェニル］－３－イル）に加えた）アダマンタン（９．９２ｇ，１６．９４ｍｍｏｌ）を添加して、透明な溶液を形成した。混合物を－４０℃に冷却し、ＢｕＬｉ（６．８４ｍＬ、１７．７９ミリモル）を滴下した。２０分間攪拌した後、混合物を冷浴から取り出し、２５分かけて周囲温度近くまで温めた。次いで混合物を－４０℃に冷却し、２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン（４．９６４ｇ、２６．６８ミリモル）の冷ヘキサン溶液（２ｍＬ）を加えた。混合物を周囲温度までゆっくり温め、次いで周囲温度で撹拌した。１時間後、濁った混合物を分液漏斗に注ぎ、水層が中性になるまで水（６×１００ｍＬ）で抽出した。有機物をブライン（２×２０ｍＬ）で抽出した。有機物をＭｇＳＯ_４で乾燥させ、濾過し、減圧下で数日間乾燥させて、生成物を無定形固体として得た。さらに精製することなく使用した。収量：９．１９７ｇ、９２．６％。 2-(3'-(adamantan-1-yl)-2'-(methoxymethoxy)-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane.

Hexane (200 mL) was added to 1-(2'-bromo-2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-3-yl)adamantane (9.92 g, 16.94 mmol) to form a clear solution. The mixture was cooled to -40°C and BuLi (6.84 mL, 17.79 mmol) was added dropwise. After stirring for 20 minutes, the mixture was removed from the cold bath and allowed to warm to near ambient temperature over 25 minutes. The mixture was then cooled to -40°C and a cold hexane solution (2 mL) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.964 g, 26.68 mmol) was added. The mixture was allowed to warm slowly to ambient temperature and then stirred at ambient temperature. After 1 h, the cloudy mixture was poured into a separatory funnel and extracted with water (6 x 100 mL) until the aqueous layer was neutral. The organics were extracted with brine (2 x 20 mL). The organics were dried over _MgSO4 , filtered, and dried under vacuum for several days to give the product as an amorphous solid. Used without further purification. Yield: 9.197 g, 92.6%.

５００ｍＬの丸底フラスコに、２－（３’－（アダマンタン－１－イル）－２’－（メトキシメトキシ）－５’－（２，４，４－トリメチルペンタン－２－イル）－［１，１’－ビフェニル］－２－イル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン（９．１９７ｇ、１５．６８ｍｍｏｌ）、２，６－ジブロモピリジン（１．７８３ｇ、７．５２５ｍｏｌ）、Ｎａ_２ＣＯ_３（４．１５４ｇ、３９．１９ｍｍｏｌ）、ジオキサン（１８０ｍＬ）および水（９０ｍＬ）を充填した。混合物を窒素で５０分間スパージし、次いで固体Ｐｄ（ＰＰｈ_３）_４（０．９０６ｇ、０．７８４ｍｍｏｌ）を添加した。混合物をさらに４０分間スパージし、次いで急速に攪拌し、１００℃に維持した油浴中で加熱した。２０時間後、揮発物を蒸発させて、黄色の泡状固体を得た。固体を砕き、水（２００ｍＬ）と共に数分間撹拌した。次に固体をフリット上に集め、水（３×２００ｍＬ）で洗浄した。次いで、黄色固体を減圧下で乾燥させた。メタノール（１００ｍＬ）、ｔｈｆ（１００ｍＬ）、および濃ＨＣｌ（７ｍＬ）を加え、混合物を６０℃に一晩加熱した。次に揮発物を蒸発させ、残留物をエーテル（２００ｍＬ）で抽出し、分液漏斗に入れた。有機物を希ＮａＨＣＯ_３（１００ｍＬ）、水（４×１５０ｍＬ）、次いでブライン（２０ｍＬ）で抽出した。有機物をＭｇＳＯ_４で乾燥させ、次いで蒸発させて、泡状の黄色固体（８．４ｇ）を得た。粗生成物をＳｉＯ_２で精製し、イソヘキサン中の１～５％ＥｔＯＡｃで溶出した。収量：４．９２ｇ、７２．０％。 2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-(2,4,4-trimethylpentan-2-yl)-[1'',1'''-biphenyl]-2-ol).

A 500 mL round bottom flask was charged with 2-(3'-(adamantan-1-yl)-2'-(methoxymethoxy)-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (9.197 g, 15.68 mmol), 2,6- _{dibromopyridine} (1.783 g, 7.525 mol), _Na2CO3 (4.154 g, 39.19 mmol), dioxane (180 mL) and water (90 mL). The mixture was sparged with nitrogen for 50 min and then solid Pd( _PPh3 ) ₄ (0.906 g, 0.784 mmol) was added. The mixture was sparged for an additional 40 minutes, then rapidly stirred and heated in an oil bath maintained at 100°C. After 20 hours, the volatiles were evaporated to give a yellow foamy solid. The solid was broken up and stirred with water (200 mL) for several minutes. The solid was then collected on a frit and washed with water (3 x 200 mL). The yellow solid was then dried under reduced pressure. Methanol (100 mL), thf (100 mL), and concentrated HCl (7 mL) were added and the mixture was heated to 60°C overnight. The volatiles were then evaporated and the residue was extracted with ether (200 mL) and placed in a separatory funnel. The organics were extracted with dilute _NaHCO3 (100 mL), water (4 x 150 mL), and then brine (20 mL). The organics were dried over _MgSO4 and then evaporated to give a foamy yellow solid (8.4 g). The crude product was purified on _SiO2 and eluted with 1-5% EtOAc in isohexane. Yield: 4.92 g, 72.0%.

ベンゼン（４ｍＬ）をＺｒＣｌ_２（ＮＭｅ_２）_２（ｄｍｅ）（０．０３７４ｇ、０．１１０ｍｍｏｌ）に添加して、わずかに濁った溶液を形成した。次に、２’，２’’’－（ピリジン－２，６－ジイル）ビス（３－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－５－（２，４，４－トリメチルペンタン－２－イル）－［１’’，１’’’－ビフェニル］－２－オール）（０．０９９８ｇ、０．１１０ｍｍｏｌ）および少量のトルエン（２ｍＬ）を加え、混合物を３５℃で撹拌した。３０分後、Ｈ ＮＭＲ分析のためにアリコートを採取し、推定される二塩化物のかなりきれいな形成を示した。次に溶液を８０℃に２５分間加熱した。揮発物を蒸発させ、残留物を減圧下で乾燥させた。残留物を熱イソヘキサン（８ｍＬ）で抽出し、濾過した。揮発性物質を蒸発させて白色固体を得て、これを減圧下、８０℃で約５分間乾燥させた。収量：０．０９４８ｇ、８０．７％。 Dichlorozirconia (2',2''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-(2,4,4-trimethylpentan-2-yl)-[1'',1'''-biphenyl]-2-olate)) (complex 66-dichloride).

Benzene (4 mL) was added to ZrCl ₂ (NMe ₂ ) ₂ (dme) (0.0374 g, 0.110 mmol) to form a slightly cloudy solution. 2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-(2,4,4-trimethylpentan-2-yl)-[1'',1'''-biphenyl]-2-ol) (0.0998 g, 0.110 mmol) and a small amount of toluene (2 mL) were then added and the mixture was stirred at 35°C. After 30 min, an aliquot was taken for H NMR analysis, which showed fairly clean formation of the presumed dichloride. The solution was then heated to 80°C for 25 min. The volatiles were evaporated and the residue was dried under reduced pressure. The residue was extracted with hot isohexane (8 mL) and filtered. The volatiles were evaporated to give a white solid which was dried under vacuum at 80° C. for about 5 minutes. Yield: 0.0948 g, 80.7%.

トルエン（６ｍＬ）を錯体３３－ジクロリド（０．０９４８ｇ、０．０８８７ミリモル）に加えて、無色透明の溶液を形成した。混合物を－１５℃に冷却し、ＭｅＭｇＢｒ（０．０９９５ｍＬ、０．３２６ミリモル）を添加した。混合物を約１５分かけて周囲温度まで温めた。１時間後、溶液を蒸発させて残留物とし、少量のイソヘキサン（１ｍＬ）を添加した。混合物を撹拌し、蒸発させた。少量のイソヘキサン（１ｍＬ）を加えて残留物を溶解し、揮発性物質を再び蒸発させた。その後、残渣を減圧乾燥した。次に残留物をイソヘキサン（１０ｍＬ）で抽出し、セライト５０３を通して濾過し、蒸発させて残留物とし、減圧下で乾燥させた。バイアルをこすり取り、錯体３３を薄茶色の固体として得られた。収量：０．０８１９ｇ、９０．０％。 Dimethylziconium (2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-(2,4,4-trimethylpentan-2-yl)-[1'',1'''-biphenyl]-2-oleate)) (complex 66).

Toluene (6 mL) was added to complex 33-dichloride (0.0948 g, 0.0887 mmol) to form a clear, colorless solution. The mixture was cooled to -15°C and MeMgBr (0.0995 mL, 0.326 mmol) was added. The mixture was allowed to warm to ambient temperature over approximately 15 minutes. After 1 hour, the solution was evaporated to a residue and a small amount of isohexane (1 mL) was added. The mixture was stirred and evaporated. A small amount of isohexane (1 mL) was added to dissolve the residue and the volatiles were evaporated again. The residue was then dried under reduced pressure. The residue was then extracted with isohexane (10 mL), filtered through Celite 503, evaporated to a residue and dried under reduced pressure. The vial was scraped to give complex 33 as a light brown solid. Yield: 0.0819 g, 90.0%.

The following complexes were used in small and large scale polymerization experiments. The complex numbers shown correspond to the Cat-ID numbers.

The following comparative complexes were used in the following small scale polymerization experiments: C-# indicates catalyst ID (Cat-ID).

Small-Scale Polymerization Examples Polymerization grade toluene and/or isohexane as solvents were obtained from ExxonMobil Chemical Company and purified through a series of columns: two 500 ^cm Oxyclear cylinders in series from Labclear (Oakland, California), followed by two 500 ^cm columns in series packed with dried 3 Å molecular sieves (8 mesh-12 mesh; Aldrich Chemical Company), and two 500 ^cm columns in series packed with dried 5 Å molecular sieves (8-12 mesh; Aldrich Chemical Company).

2-Norbornene (NB, Aldrich Chemical Company) was diluted with toluene, sparged with nitrogen, and passed through a column of Brockmann basic alumina (Aldrich Chemical Company). The final solution concentration was 42 wt% or 78 wt% in toluene. Cyclopentene (cP, Aldrich Chemical Company) was purged with nitrogen, passed through a column of neutral alumina, and stored over molesieves. Tri(n-octyl)aluminum (TNOA or TnOAl) was purchased from Aldrich Chemical Company or Akzo Nobel and used as received.

Polymerization grade ethylene was further purified by passage through a series of columns: a 500 ^cm Oxyclear cylinder from Labclear (Oakland, California), followed by a 500 cm ^column packed with dried 3 Å molecular sieves (8 mesh-12 mesh; Aldrich Chemical Company), and ^a 500 cm column packed with dried 5 Å molecular sieves (8 mesh-12 mesh; Aldrich Chemical Company).

Polymerization grade propylene was further purified by passing through a series of columns: a Labclear 2,250 cm ³ Oxyclear cylinder, followed by a 2,250 cm ³ column packed with 3 Å molecular sieves (8 mesh-12 mesh; Aldrich Chemical Company), then a 50 cm 3 column packed with 5 Å molecular sieves (8 mesh-12 mesh; Aldrich Chemical Company).
0 ^cm3 column, a 500 ^cm3 column packed with Selexsorb CD (BASF) and finally a 500 ^cm3 column packed with Selexsorb COS (BASF).

N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate was purchased from Boulder Scientific or WRGrace. N,N-Dimethylanilinium tetrakis(perfluoronaphthalen-2-yl)borate was purchased from WRGrace. All complexes and activators were added to the reactor as dilute solutions in toluene. The concentrations of activator, scavenger, and complex solutions added to the reactor were selected to ensure accurate delivery, between 40 microliters and 200 microliters of solution were added to the reactor.

Reactor Description and Preparation Polymerizations were carried out in an autoclave in an inert atmosphere ( _N2 ) drybox. The autoclave was equipped with an external heater for temperature control, a glass insert (internal reactor volume = 23.5 mL for runs with _C2 and 22.5 mL for runs with _C3 ), a septum inlet to regulate the nitrogen, ethylene, propylene feeds, and a disposable polyetheretherketone mechanical stirrer (800 RPM). The autoclave was prepared by purging with dry nitrogen at 110°C or 115°C for 5 hours, then at 25°C for 5 hours.

Ethylene polymerization (PE), ethylene/cyclic olefin copolymerization (E - cP or E - NB) and cyclic olefin homopolymerization (p - cP)
The reactor was prepared as above and then purged with ethylene or, in the case of reactors not using ethylene, with nitrogen. Isohexane (solvent unless otherwise noted) and cyclic comonomer were added via syringe at room temperature and atmospheric pressure. The reactor was then brought to process temperature (typically 100° C.) and charged with ethylene (if used) while stirring at 800 RPM. A scavenger solution (e.g., TNOA in isohexane or toluene) was then added via syringe to the reactor at process conditions. A non-coordinating activator (e.g., N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate) solution (in toluene) was added via syringe to the reactor at process conditions, followed by the addition of the pre-catalyst (i.e., complex or catalyst identified by Cat ID). The solution (in toluene) was injected via syringe into the reactor at process conditions. If used, ethylene was admitted to the autoclave (using a computer-controlled solenoid valve) to maintain the reactor gauge pressure (+/- 2 psi) during polymerization. The reactor temperature was monitored and typically maintained within ±1°C. Polymerization was stopped by adding a compressed dry air mixture at about 50 psi to the autoclave for about 30 seconds. Polymerization was quenched after addition of a predetermined cumulative amount of ethylene (if used) or for the maximum minutes of polymerization time. The reactor was cooled and vented. The polymer was isolated after removal of the solvent in vacuum. The reported yield includes the total weight of polymer and residual catalyst. Catalyst activity is reported as grams of polymer per millimole of transition metal compound per hour of reaction time (g/mmol/hr). "C#" indicates a comparative example. Microliters (μl or μL) may be reported as uL or ul in the tables below.

Propylene polymerization (PP) and propylene/cyclic olefin copolymerization (P - cP or P - NB)
The reactor was prepared as described above, then heated to 40° C. and purged with propylene gas at atmospheric pressure. Isohexane (solvent unless otherwise noted), cyclic comonomer, and liquid propylene were added via syringe. The reactor was then heated to process temperature (typically 100° C.) with stirring at 800 RPM. A scavenger solution (e.g., TNOA in isohexane or toluene) was then added to the reactor at process conditions via syringe. A non-coordinating activator (e.g., N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate or N,N-dimethylanilinium tetrakis(perfluoronaphthalen-2-yl)borate) solution (in toluene) was then added to the reactor at process conditions via syringe. A precatalyst (i.e., complex or catalyst identified by catalyst ID) solution (in toluene) was subsequently injected into the reactor via syringe at process conditions. The reactor temperature was monitored and typically maintained within ±1° C. Polymerizations were stopped by adding a compressed dry air (alternatively, _CO2 when mentioned) gas mixture at about 50 psi to the autoclave for about 30 seconds unless otherwise stated. Polymerizations were quenched based on a predetermined pressure drop of about 8 psi (unless otherwise stated) or based on a maximum polymerization time of 30 minutes (unless otherwise stated). The reactor was cooled and vented. The polymer was isolated after removing the solvent in vacuum. The reported yield includes the total weight of polymer and residual catalyst. Catalyst activity can usually be reported as grams of polymer per mmol of transition metal compound per hour of reaction time (g/mmol/hr).

The quench time (s, seconds) is the actual time of polymerization, determined by the maximum uptake (quench value) or maximum quench time shown. The quench value (psi) is the set value of ethylene uptake for polymerizations with ethylene, or the total pressure loss for polymerizations without ethylene. The maximum reaction (rxn) time is the set value of the maximum time that the polymerization can run if it has not already been quenched by uptake.

For small scale polymer characterization analytical testing, polymers were prepared by dissolving in 1,2,4-trichlorobenzene (TCB, from Aldrich, 99+%) containing 2,6-di-tert-butyl-4-methylphenol (BHT, from Aldrich, 99%) for approximately 3 hours in a shaker oven at 165°C. Typical concentrations of polymer in solution were 0.1-0.9 mg/mL with a BHT concentration of 1.25 mg BHT/mL of TCB. Samples were cooled to 135°C for testing.

High temperature size exclusion chromatography was performed using an automated "Rapid GPC" system as described in U.S. Patent Nos. 6,491,816; 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388; each of which is incorporated herein by reference. Molecular weights (weight average (Mw), number average (Mn), z-average (Mz)) and molecular weight distributions (PDI=MWD=Mw/Mn), also referred to as polymer polydispersity (PDI), were measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector (ELSD) and calibrated using polystyrene standards (Polymer Laboratories: Polystill Calibration Kit SM-10: Mp (peak Mw) 5,000-3,390,000). Alternatively, samples were measured by gel permeation chromatography using a Symyx Technology GPC equipped with a dual wavelength infrared detector and calibrated with polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) 580-3,039,000). Samples (250 μL of polymer solution in TCB was injected into the system) were analyzed using three Polymer Laboratories: PLgel 10 μm Mixed-B 300×7.5 mm columns in series with an eluent flow rate of 2.0 ml/min (sample temperature 135° C., oven/column 165° C.). No column diffusion correction was performed. Numerical analysis was performed using Epoch® software available from Symyx Technologies or Automation Studio software available from Freeslate. Molecular weights obtained are relative to linear polystyrene standards. Molecular weight data are reported in the following table in Mn, Mw, Mz, and PDI, as defined above.

Differential scanning calorimetry (DSC) measurements were performed using a TA-Q100 instrument to determine the melting points of the polymers. The samples were pre-annealed at 220° C. for 15 minutes (first melt) and then cooled to room temperature overnight. The samples were then heated to 220° C. at a rate of 100° C./min (second melt) and then cooled at a rate of 50° C./min. Melting points were collected during the heating period. The reported value is the peak melting temperature, also referred to as the second melt for purposes of this disclosure. The results are reported in the table below as T _m .

Ｅ＝エチレン、Ｃｐ＝シクロペンテン、１０００Ｃ＝１０００主鎖炭素
この計算は、Ｃｐの１，２付加に用いれる。 ¹ H NMR Measurement of Ethylene-Cyclopentene Copolymer:
Unless otherwise stated, ethylene-cyclopentene (E-Cp) samples for ¹ H NMR spectroscopy were dissolved in 1,1,2,2-tetrachloroethane-d2 (tc-d2) at 140° C. at a concentration of 30 mg/mL. Samples were run on a Bruker NMR spectrometer at 120° C. NMR measurements were performed using ^{a 1} H NMR frequency of 600 MHz or higher, a 30° pulse using a 10 mm cryoprobe, at least 512 scans, and a 5 second delay. Chemical shifts of E-Cp were referenced to the solvent tc-d2 at 5.98 ppm.

E = ethylene, Cp = cyclopentene, 1000C = 1000 main chain carbons. This calculation is used for the 1,2 addition of Cp.

^1H NMR measurement of polycyclopentene:
Unless otherwise noted, polycyclopentene (polyCp) samples for ¹ H NMR spectroscopy were dissolved in 1,1,2,2-tetrachloroethane-d2 (tc-d2) at a concentration of 30 mg/mL at 140° C. Samples were run on a Bruker NMR spectrometer at 120° C. NMR runs were performed at ^{a 1} H NMR frequency of 500 MHz or higher, a 30° pulse, at least 512 scans, and a 5 second delay. Chemical shifts of polyCp were referenced to the solvent tc-d2 at 5.98 ppm.

¹ H NMR Measurement of Ethylene-Norbornene (E-MB) Polymer:
Unless otherwise stated, ethylene-norbornene copolymer (E-NB) samples for ¹ H NMR spectroscopy were dissolved in 1,1,2,2-tetrachloroethane-d2 at a concentration of 30 mg/mL at 140° C. Samples were measured on a Bruker NMR spectrometer at 120° C. NMR measurements were performed at ^{a 1} H NMR frequency of 600 MHz or higher, a 3° pulse, 512 scans, and a 15 second delay.

^13C NMR measurement of copolymer:
Unless otherwise stated, copolymer samples for ^13C NMR spectroscopy (E-Cp, PP-Cp, E-NB, and PP-NB) were dissolved in 1,1,2,2-tetrachloroethane-d2 (tc-d2) at 140°C to concentrations between 33 and 67 mg/mL. Samples were measured using a Bruker NMR spectrometer at 120°C. NMR measurements were performed using a 10 mm cryoprobe with ^13C frequencies of 150 MHz or higher, gated decoupling with a 90° pulse, at least 512 transients, and a 10 second delay. For ethylene-based polymers, chemical shifts were referenced to the major PE peak at 29.98 ppm, and for propylene-based polymers, chemical shifts were referenced to the major isotactic _CH3 peak at 21.83 ppm.

Ethylene-cyclopentene copolymer (E-Cp):
Assignments and base calculations for 1,3 cis and 1,3 trans additions of cyclopentene, and 1,2 additions of cyclopentene in ethylene-cyclopentene copolymers were taken from M. Napoli et.al. "Copolymerization of Ethylene with Cyclopentene or 2-butene with Half Titanocenes-Based Catalysts" Journal of Polymer Science A: Polymer Chemistry, v.46, pp. 4725-4733, (2008).

The assignments and nomenclature of 1,2 additions of cyclopentene-ethylene copolymers were taken from A. Jerschow et.al. "Nuclear Magnetic Resonance Evidence for a new Microstructure in Ethene-Cyclopentene Copolymers" Macromolecules, v.28, pp. 7095-7099, (1995). c = Cp, e = ethylene

The 1,2 addition sequence distributions, where the triad distributions are denoted as ccc, ece, and cce.

Propylene-cyclopentene copolymer (P-Cp):
The assignments and nomenclature of propylene-cyclopentene (P-Cp) are based on N. Naga, Y. Imanishi, "Structure of cyclopentene unit in the copolymer with propylene obtained by stereospecific zirconocene catalysts" Polymer, v.43, pp. 2133-2139, (2002). These assignments are for 1,2 addition only.

Ethylene-norbornene copolymer (E-NB):
Calculation of E-NB (ethylene-norbornene) composition (mol%) and assignment and quantification of composition distribution (isolated, alternating, block-like) are based on Bergstrom et.al. "Influence of Polymerization Conditions on Microstructure of Norbornene-Ethylene Copolymers Made Using Metallocene Catalysts and MAO" Journal of Applied Polymer Science, v.63, pp. 1071-1076, (1997).

Propylene-norbornene copolymer (P-NB):
The assignment and numbering of P-NB (propylene-norbornene) is based on I. Tritto et.al. "Propene-Norbornene Copolymers: Synthesis and Analysis of Polymer Structure by 13C NMR Spectroscopy and ab Initio Chemical Shift Computations" Macromolecules, v.36, pp. 882-890 (2003). The composition (mol%) was calculated as follows.

Large-scale polymerization

Polymerizations were carried out in a continuous stirred tank reactor system. A 1 liter autoclave reactor was fitted with a water cooling/steam heating element with an agitator, pressure controller, and temperature controller. The reactor was operated in a liquid-filled state with the reactor pressure above the boiling point pressure of the reactant mixture to maintain the reactants in the liquid phase. Isohexane was pumped into the reactor by a Pulsa feed pump, the flow rate of which was controlled using a Coriolis mass flow controller (Quantim series from Brooks). Norbornene (Sigma Aldrich) was dissolved in toluene to form a solution of approximately 85.3 wt.%. The solution was fed to the reactor using a metering pump. Ethylene flowed as a gas under its own pressure through a Brooks flow controller. The monomers (e.g., ethylene and norbornene) were combined into one stream and then mixed with the isohexane stream. The mixture was then fed to the reactor through a single line. A scavenger solution was added to the combined solvent and monomer stream just before the reactor to further reduce catalyst poisons. Similarly, the catalyst solution was fed to the reactor through a separate line using an ISCO syringe pump. Isohexane (used as solvent), as well as the norbornene solution and ethylene, were purified over alumina beds and molecular sieves. Toluene for preparing the catalyst solution was similarly purified. Unless otherwise stated, all reactions were carried out at a pressure of approximately 2.4 MPa/g.

A solution of tri-n-octylaluminum (TNOA) in isohexane (25 wt % in hexane, Sigma Aldrich) was used as the scavenger solution. Catalyst solutions were prepared by mixing precatalyst (complex 6 or comparative complex C-7) with N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (A1) in a molar ratio of about 1:1 in 900 ml of toluene or with (hydrogenated tallow alkyl)methylammonium tetra(pentafluorophenyl)borate (A2, 10 wt % in methylcyclohexane) in a molar ratio of about 1:1 in 900 ml of toluene. Both activators are available from Boulder Scientific Company.

The polymer produced in the reactor was discharged through a back pressure control valve that reduced the pressure to atmospheric pressure. This caused the unconverted monomers in the solution to evaporate into a vapor phase and discharged from the top of the gas-liquid separator. The liquid phase, which mainly contained the polymer and the solvent, was collected to recover the polymer. The collected samples were first precipitated using isopropyl alcohol and stabilized using IRGANOX 1076 (available from BASF), and then dried in a vacuum oven at a temperature of about 90° C. for about 12 hours. The vacuum oven dried samples were weighed to obtain the yield. Tg was measured using DSC and norbornene content was measured using proton NMR as described above. The detailed polymerization conditions for Examples G1-G20 are shown in Tables 8-10 below.

All documents described herein, including priority documents and/or testing procedures, are incorporated herein by reference unless inconsistent with this document. As is apparent from the general description and specific embodiments above, embodiments of the present invention have been illustrated and described, but various modifications can be made without departing from the spirit and scope of the present invention. Accordingly, the present invention is not intended to be limited by the above. Similarly, the term "comprising" is considered to be synonymous with the term "including". Similarly, whenever the transitional phrase "comprising" appears before a composition, element, or group of elements, it is understood that the same composition or group of elements may also be considered to include the transitional phrases "consisting essentially of," "consisting of," "selected from the group of consisting of," or "is" before the composition, element, or element, and vice versa.

Certain embodiments and features have been described using a set of upper numerical limits and a set of lower numerical limits. It should be understood that ranges including combinations of any two values are contemplated, for example, any combination of any lower limit with any upper limit, any combination of any two lower limits, and/or any combination of any two upper limits, unless otherwise specified. Specific lower limits, upper limits, and ranges are set forth in one or more claims below. All numerical values are "about" or "approximately" the indicated value and account for experimental error and variations that would be expected by one of ordinary skill in the art.

Claims (12)

A cyclic olefin monomer and an optional comonomer selected from a _C2 - _C20 alpha olefin are reacted with an activator and a copolymer having the formula (I):

[Wherein:
M is Hf or Zr;
E and E' are O;
A ¹ QA ^{1 '} is a portion of a substituted or unsubstituted pyridine ring, where Q is N, A ¹ and A ^{1 '} are independently C or C(R ²² ), and R ²² is selected from hydrogen, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ substituted hydrocarbyl;

is part of a substituted or unsubstituted benzene ring or of a benzothiophene or indole heterocycle;

is part of a substituted or unsubstituted benzene ring or of a benzothiophene or indole heterocycle;
L is a Lewis base;
X is an anionic ligand;
n is 1, 2 or 3;
m is 0, 1, or 2;
n+m is 4 or less;
R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^2' , R ^3' , and R ^4' are each independently hydrogen, a C ₁ -C ₄₀ hydrocarbyl, a C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group;
one or more of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^1′ and R ^2′ , R ^2′ and R ^3′ , R ^3′ and R ^4′ may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, where substitutions on the rings may be joined to form additional rings;
Any two L groups may be combined to form a bidentate Lewis base;
The X group may be attached to the L group to form a monoanionic bidentate group;
Any two X groups may be combined to form a dianionic ligand.
A process for polymerization comprising contacting a catalyst system comprising a catalyst compound represented by The catalyst compound has the formula (II):

[Wherein:
M is Hf or Zr;
E and E' are O;
Each L is independently a Lewis base;
Each X is independently an anionic ligand;
n is 1, 2 or 3;
m is 0, 1, or 2;
n+m is 4 or less;
R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^2' , R ^3' , and R ^4' are each independently hydrogen, a C ₁ -C ₄₀ hydrocarbyl, a C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group;
one or more of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^1′ and R ^2′ , R ^2′ and R ^3′ , R ^3′ and R ^4′ may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, where substitutions on the rings may be joined to form additional rings;
Any two L groups may be combined to form a bidentate Lewis base;
The X group may be attached to the L group to form a monoanionic bidentate group;
Any two X groups may be combined to form a dianionic ligand;
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^5' , R ^6' , R ^7' , R ^8' , R ¹⁰ , R ¹¹ , and R ¹² are each independently hydrogen, a C ₁ -C ₄₀ hydrocarbyl, a C ₁ -C ₄₀ substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group;
One or more ^{of R5} and ^R6 , ^R6 and ^R7 , ^R7 and ^R8 , R5 ^' and R6 ^' , R6 ^' and ^R7' , R7 ^' and R8 ^' , ^R10 and ^R11 , or ^R11 and ^R12 may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings, each having 5, 6, 7, or 8 ring atoms, where substitutions on the rings may be joined to form additional rings.
The method of claim 1 , wherein the The method of claim 1 or 2, wherein R ¹ and R ^1' are each independently a C ₄ to C ₄₀ tertiary hydrocarbyl group, or a C ₄ to C ₄₀ cyclic tertiary hydrocarbyl group. each X is independently a monovalent radical derived from a compound or structure selected from the group consisting of a substituted or unsubstituted hydrocarbyl radical having 1 to 20 carbon atoms, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halide, and combinations thereof (two Xs may form part of a fused ring or ring system);
each L is independently a monovalent radical derived from a compound or structure selected from the group consisting of ethers, thioethers, amines, phosphines, ethyl ethers, tetrahydrofuran, dimethylsulfide, triethylamine, pyridine, alkenes, alkynes, allenes, and carbenes, and combinations thereof (optionally, two or more L may form part of a fused ring or ring system);
The method according to any one of claims 1 to 3. Both R ¹ and R ^1' are C ₄ -C ₂₀ cyclic tertiary alkyl, adamantan-1-yl or substituted adamantan-1-yl;
The method of claim 1. X is methyl or chloro and n is 2;
The method of claim 1. The catalyst compound has the formula:

The method of claim 1 , wherein the compound is one or more compounds represented by The catalyst compound has the formula:

The method of claim 1 , wherein the compound is one or more compounds represented by The activator has the formula:

wherein A ^d− is a non-coordinating anion having a charge d−; d is an integer from 1 to 3; and (Z) _d ⁺ is

]
The method according to any one of claims 1 to 8, wherein the compound is represented by The method according to any one of claims 1 to 3, further comprising recovering a polymer containing at least 0.1 mol % of a cyclic olefin as a polymer building block. The method according to any one of claims 1 to 3, further comprising recovering a polymer comprising at least 1 mol% cyclic olefin as a polymer building block and at least 20 mol% ethylene or at least 20 mol% propylene as a polymer building block. The method of any one of claims 1 to 3, wherein the cyclic olefin monomer comprises at least one selected from substituted or unsubstituted cyclopentene and substituted or unsubstituted 2-norbornene .